965 resultados para ASSOCIATIVE IONIZATION
Resumo:
The purpose of the current article is to support the investigation of linguistic relativity in second language acquisition and sketch methodological and theoretical prerequisites toward developing the domain into a full research program. We identify and discuss three theoretical-methodological components that we believe are needed to succeed in this enterprise. First, we highlight the importance of using nonverbal methods to study linguistic relativity effects in second language (L2) speakers. The use of nonverbal tasks is necessary in order to avoid the circularity that arises when inferences about nonverbal behavior are made on the basis of verbal evidence alone. Second, we identify and delineate the likely cognitive mechanisms underpinning cognitive restructuring in L2 speakers by introducing the theoretical framework of associative learning. By doing so, we demonstrate that the extent and nature of cognitive restructuring in L2 speakers is essentially a function of variation in individual learners’ trajectories. Third, we offer an in-depth discussion of the factors (e.g., L2 proficiency and L2 use) that characterize those trajectories, anchoring them to the framework of associative learning, and reinterpreting their relative strength in predicting L2 speaker cognition
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Solar energetic particles (SEPs) occasionally contribute additional atmospheric ionization beyond that arising from the usual galactic cosmic ray background. During an SEP event associated with a solar flare on April 11, 2013, the vertical ionization rate profile obtained using a balloon-borne detector showed enhanced ionization with a 26% increase at 20 km, over Reading, United Kingdom. Fluctuations in atmospheric electrical parameters were also detected at the surface, beneath the balloon’s trajectory. As no coincident changes in geomagnetism occurred, the electrical fluctuations are very likely to be associated with increased ionization, as observed by the balloon measurements. The lack of response of surface neutron monitors during this event indicates that energetic particles that are not detected at the surface by neutron monitors can nevertheless enter and influence the atmosphere’s weather-generating regions.
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Objective. The main purpose of the study was to examine whether emotion impairs associative memory for previously seen items in older adults, as previously observed in younger adults. Method. Thirty-two younger adults and 32 older adults participated. The experiment consisted of 2 parts. In Part 1, participants learned picture–object associations for negative and neutral pictures. In Part 2, they learned picture–location associations for negative and neutral pictures; half of these pictures were seen in Part 1 whereas the other half were new. The dependent measure was how many locations of negative versus neutral items in the new versus old categories participants remembered in Part 2. Results. Both groups had more difficulty learning the locations of old negative pictures than of new negative pictures. However, this pattern was not observed for neutral items. Discussion. Despite the fact that older adults showed overall decline in associative memory, the impairing effect of emotion on updating associative memory was similar between younger and older adults.
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During many magnetospheric substorms, the auroral oval near midnight is observed to expand poleward in association with strong negative perturbations measured by local ground magnetometers. We show Sondrestrom and EISCAT incoherent scatter radar measurements during three such events. In each of the events, enhanced ionization produced by the precipitation moved northward by several degrees of latitude within 10–20 min. The electric fields measured during the three events were significantly different. In one event the electric field was southward everywhere within the precipitation region. In the other two events a reversal in the meridional component of the field was observed. In one case the reversal occurred within the precipitation region, while in the other case the reversal was at the poleward boundary of the precipitation. The westward electrojet that produces the negative H-perturbation in the ground magnetic field has Hall and Pedersen components to varying degrees. In one case the Hall component was eastward and the Pedersen component was westward, but the net magnetic H-deflection on the ground was negative. Simultaneous EISCAT measurements made near the dawn meridian during one of the events show that the polar cap boundary moved northward at the same time as the aurora expanded northward at Sondrestrom. Most of the differences in the electrodynamic configuration in the three events can be accounted for in terms of the location at which the measurements were made relative to the center of the auroral bulge.
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Calculations using a numerical model of the convection dominated high latitude ionosphere are compared with observations made by EISCAT as part of the UK-POLAR Special Programme. The data used were for 24–25 October 1984, which was characterized by an unusually steady IMF, with Bz < 0 and By > 0; in the calculations it was assumed that a steady IMF implies steady convection conditions. Using the electric field models of Heppner and Maynard (1983) appropriate to By > 0 and precipitation data taken from Spiroet al. (1982), we calculated the velocities and electron densities appropriate to the EISCAT observations. Many of the general features of the velocity data were reproduced by the model. In particular, the phasing of the change from eastward to westward flow in the vicinity of the Harang discontinuity, flows near the dayside throat and a region of slow flow at higher latitudes near dusk were well reproduced. In the afternoon sector modelled velocity values were significantly less than those observed. Electron density calculations showed good agreement with EISCAT observations near the F-peak, but compared poorly with observations near 211 km. In both cases, the greatest disagreement occurred in the early part of the observations, where the convection pattern was poorly known and showed some evidence of long term temporal change. Possible causes for the disagreement between observations and calculations are discussed and shown to raise interesting and, as yet, unresolved questions concerning the interpretation of the data. For the data set used, the late afternoon dip in electron density observed near the F-peak and interpreted as the signature of the mid-latitude trough is well reproduced by the calculations. Calculations indicate that it does not arise from long residence times of plasma on the nightside, but is the signature of a gap between two major ionization sources, viz. photoionization and particle precipitation.
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The propagation of 7.335 MHz, c.w. signals over a 5212 km sub-auroral, west-east path is studied. Measurements and semi-empirical predictions are made of the amplitude distributions and Doppler shifts of the received signals. The observed amplitude distribution is fitted with one produced by a numerical fading model, yielding the power losses suffered by the signals during propagation via the predominating modes. The signals are found to suffer exceptionally low losses at certain local times under geomagnetically quiet conditions. The mid-latitude trough in the F2 peak ionization density is predicted by a statistical model to be at the latitudes of this path at these times and at low Kp values. A sharp cut-off in low-power losses at a mean Kp of 2.75 strongly implicates the trough in the propagation of these signals. The Doppler shifts observed at these times cannot be explained by a simple ray-tracing model. It is shown however, that a simple extension of this model to allow for the trough can reproduce the form of the observed diurnal variation.
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The chemisorption of CH4 on Pt{110}-(1 x 2) has been studied by vibrational analysis of the reaction pathway defined by the potential energy surface and, in time reversal, by first-principles molecular dynamics simulations of CH4 associative desorption, with the electronic structure treated explicitly using density functional theory. We find that the symmetric stretch vibration ν1 is strongly coupled to the reaction coordinate; our results therefore provide a firm theoretical basis for recently reported state-resolved reactivity measurements, which show that excitation of the ν1 normal mode is the most efficient way to enhance the reaction probability
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Tracking the formation and full evolution of polar cap ionization patches in the polar ionosphere, we directly observe the full Dungey convection cycle for southward interplanetary magnetic field (IMF) conditions. This enables us to study how the Dungey cycle influences the patches’ evolution. The patches were initially segmented from the dayside storm enhanced density plume at the equatorward edge of the cusp, by the expansion and contraction of the polar cap boundary due to pulsed dayside magnetopause reconnection, as indicated by in situ Time History of Events and Macroscale Interactions during Substorms(THEMIS) observations. Convection led to the patches entering the polar cap and being transported antisunward, while being continuously monitored by the globally distributed arrays of GPS receivers and Super Dual Auroral Radar Network radars. Changes in convection over time resulted in the patches following a range of trajectories, each of which differed somewhat from the classical twin-cell convection streamlines. Pulsed nightside reconnection, occurring as part of the magnetospheric substorm cycle, modulated the exit of the patches from the polar cap, as confirmed by coordinated observations of the magnetometer at Tromsø and European Incoherent Scatter Tromsø UHF radar. After exiting the polar cap, the patches broke up into a number of plasma blobs and returned sunward in the auroral return flow of the dawn and/or dusk convection cell. The full circulation time was about 3 h.
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The ‘soft’ ionization technique matrix-assisted laser desorption/ionization (MALDI) is without doubt one of the great success stories of modern mass spectrometry (MS). In particular, the further development of MALDI and in general ‘soft’ laser ionization, focusing on their unique characteristics and advantages in areas such as speed, spatial resolution, sample preparation and low spectral complexity, have led to great advances in mass spectral profiling and imaging with an extremely auspicious future in (bio)medical analyses.
Resumo:
Although liquid matrix-assisted laser desorption/ionization (MALDI) has been used in mass spectrometry (MS) since the early introduction of MALDI, its substantial lack of sensitivity compared to solid (crystalline) MALDI was for a long time a major hurdle to its analytical competitiveness. In the last decade, this situation has changed with the development of new sensitive liquid matrices, which are often based on a binary matrix acid/base system. Some of these matrices were inspired by the recent progress in ionic liquid research, while others were developed from revisiting previous liquid MALDI work as well as from a combination of these two approaches. As a result, two high-performing liquid matrix classes have been developed, the ionic liquid matrices (ILMs) and the liquid support matrices (LSMs), now allowing MS measurements at a sensitivity level that is very close to the level of solid MALDI and in some cases even surpasses it. This chapter provides some basic information on a selection of highly successful representatives of these new liquid matrices and describes in detail how they are made and applied in MALDI MS analysis.
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Matrix-assisted laser desorption/ionisation (MALDI) coupled with time-of-flight (TOF) mass spectrometry (MS) is a powerful tool for the analysis of biological samples, and nanoflow high-performance liquid chromatography (nanoHPLC) is a useful separation technique for the analysis of complex proteomics samples. The off-line combination of MALDI and nanoHPLC has been extensively investigated and straightforward techniques have been developed, focussing particularly on automated MALDI sample preparation that yields sensitive and reproducible spectra. Normally conventional solid MALDI matrices such as α-cyano-4-hydroxycinnamic acid (CHCA) are used for sample preparation. However, they have limited usefulness in quantitative measurements and automated data acquisition because of the formation of heterogeneous crystals, resulting in highly variable ion yields and desorption/ ionization characteristics. Glycerol-based liquid support matrices (LSM) have been proposed as an alternative to the traditional solid matrices as they provide increased shot-to-shot reproducibility, leading to prolonged and stable ion signals and therefore better results. This chapter focuses on the integration of the liquid LSM MALDI matrices into the LC-MALDI MS/MS approach in identifying complex and large proteomes. The interface between LC and MALDI consists of a robotic spotter, which fractionates the eluent from the LC column into nanoliter volumes, and co-spots simultaneously the liquid matrix with the eluent fractions onto a MALDI target plate via sheath flow. The efficiency of this method is demonstrated through the analysis of trypsin digests of both bovine serum albumin (BSA) and Lactobacillus plantarum WCFS1 proteins.
Investigation and optimization of parameters affecting the multiply charged ion yield in AP-MALDI MS
Resumo:
Liquid matrix-assisted laser desorption/ionization (MALDI) allows the generation of predominantly multiply charged ions in atmospheric pressure (AP) MALDI ion sources for mass spectrometry (MS) analysis. The charge state distribution of the generated ions and the efficiency of the ion source in generating such ions crucially depend on the desolvation regime of the MALDI plume after desorption in the AP-tovacuum inlet. Both high temperature and a flow regime with increased residence time of the desorbed plume in the desolvation region promote the generation of multiply charged ions. Without such measures the application of an electric ion extraction field significantly increases the ion signal intensity of singly charged species while the detection of multiply charged species is less dependent on the extraction field. In general, optimization of high temperature application facilitates the predominant formation and detection of multiply charged compared to singly charged ion species. In this study an experimental setup and optimization strategy is described for liquid AP-MALDI MS which improves the ionization effi- ciency of selected ion species up to 14 times. In combination with ion mobility separation, the method allows the detection of multiply charged peptide and protein ions for analyte solution concentrations as low as 2 fmol/lL (0.5 lL, i.e. 1 fmol, deposited on the target) with very low sample consumption in the low nL-range.
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We report simultaneous global monitoring of a patch of ionization and in situ observation of ion upflow at the center of the polar cap region during a geomagnetic storm. Our observations indicate strong fluxes of upwelling O+ ions originating from frictional heating produced by rapid antisunward flow of the plasma patch. The statistical results from the crossings of the central polar cap region by Defense Meteorological Satellite Program F16–F18 from 2010 to 2013 confirm that the field-aligned flow can turn upward when rapid antisunward flows appear, with consequent significant frictional heating of the ions, which overcomes the gravity effect. We suggest that such rapidly moving patches can provide an important source of upwelling ions in a region where downward flows are usually expected. These observations give new insight into the processes of ionosphere-magnetosphere coupling.
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The self-assembly in aqueous solution of three novel telechelic conjugates comprising a central hydrophilic polymer and short (trimeric or pentameric) tyrosine end-caps has been investigated. Two of the conjugates have a central poly(oxyethylene) (polyethylene oxide, PEO) central block with different molar masses. The other conjugate has a central poly(l-alanine) (PAla) sequence in a purely amino-acid based conjugate. All three conjugates self-assemble into β-sheet based fibrillar structures, although the fibrillar morphology revealed by cryogenic-TEM is distinct for the three polymers—in particular the Tyr5-PEO6k-Tyr5 forms a population of short straight fibrils in contrast to the more diffuse fibril aggregates observed for Tyr5-PEO2k-Tyr5 and Tyr3-PAla-Tyr3. Hydrogel formation was not observed for these samples (in contrast to prior work on related systems) up to quite high concentrations, showing that it is possible to prepare solutions of peptide–polymer-peptide conjugates with hydrophobic end-caps without conformational constraints associated with hydrogelation. The Tyr5-PEO6k-Tyr5 shows significant PEO crystallization upon drying in contrast to the Tyr5-PEO2k-Tyr5 conjugate. Our findings point to the remarkable ability of short hydrophobic peptide end groups to modulate the self-assembly properties of polymers in solution in model peptide-capped “associative polymers”. Retention of fluidity at high conjugate concentration may be valuable in potential future applications of these conjugates as bioresponsive or biocompatible materials, for example exploiting the enzyme-responsiveness of the tyrosine end-groups