983 resultados para surface electronic phenomena


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The three-dimensional documentation of footwear and tyre impressions in snow offers an opportunity to capture additional fine detail for the identification as present photographs. For this approach, up to now, different casting methods have been used. Casting of footwear impressions in snow has always been a difficult assignment. This work demonstrates that for the three-dimensional documentation of impressions in snow the non-destructive method of 3D optical surface scanning is suitable. The new method delivers more detailed results of higher accuracy than the conventional casting techniques. The results of this easy to use and mobile 3D optical surface scanner were very satisfactory in different meteorological and snow conditions. The method is also suitable for impressions in soil, sand or other materials. In addition to the side by side comparison, the automatic comparison of the 3D models and the computation of deviations and accuracy of the data simplify the examination and delivers objective and secure results. The results can be visualized efficiently. Data exchange between investigating authorities at a national or an international level can be achieved easily with electronic data carriers.

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The existence and morphology, as well as the dynamics of micro-scale gas-liquid interfaces is investigated numerically and experimentally. These studies can be used to assess liquid management issues in microsystems such as PEMFC gas flow channels, and are meant to open new research perspectives in two-phase flow, particularly in film deposition on non-wetting surfaces. For example the critical plug volume data can be used to deliver desired length plugs, or to determine the plug formation frequency. The dynamics of gas-liquid interfaces, of interest for applications involving small passages (e.g. heat exchangers, phase separators and filtration systems), was investigated using high-speed microscopy - a method that also proved useful for the study of film deposition processes. The existence limit for a liquid plug forming in a mixed wetting channel is determined by numerical simulations using Surface Evolver. The plug model simulate actual conditions in the gas flow channels of PEM fuel cells, the wetting of the gas diffusion layer (GDL) side of the channel being different from the wetting of the bipolar plate walls. The minimum plug volume, denoted as critical volume is computed for a series of GDL and bipolar plate wetting properties. Critical volume data is meant to assist in the water management of PEMFC, when corroborated with experimental data. The effect of cross section geometry is assessed by computing the critical volume in square and trapezoidal channels. Droplet simulations show that water can be passively removed from the GDL surface towards the bipolar plate if we take advantage on differing wetting properties between the two surfaces, to possibly avoid the gas transport blockage through the GDL. High speed microscopy was employed in two-phase and film deposition experiments with water in round and square capillary tubes. Periodic interface destabilization was observed and the existence of compression waves in the gas phase is discussed by taking into consideration a naturally occurring convergent-divergent nozzle formed by the flowing liquid phase. The effect of channel geometry and wetting properties was investigated through two-phase water-air flow in square and round microchannels, having three static contact angles of 20, 80 and 105 degrees. Four different flow regimes are observed for a fixed flow rate, this being thought to be caused by the wetting behavior of liquid flowing in the corners as well as the liquid film stability. Film deposition experiments in wetting and non-wetting round microchannels show that a thicker film is deposited for wetting conditions departing from the ideal 0 degrees contact angle. A film thickness dependence with the contact angle theta as well as the Capillary number, in the form h_R ~ Ca^(2/3)/ cos(theta) is inferred from scaling arguments, for contact angles smaller than 36 degrees. Non-wetting film deposition experiments reveal that a film significantly thicker than the wetting Bretherton film is deposited. A hydraulic jump occurs if critical conditions are met, as given by a proposed nondimensional parameter similar to the Froude number. Film thickness correlations are also found by matching the measured and the proposed velocity derived in the shock theory. The surface wetting as well as the presence of the shock cause morphological changes in the Taylor bubble flow.

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In power electronic basedmicrogrids, the computational requirements needed to implement an optimized online control strategy can be prohibitive. The work presented in this dissertation proposes a generalized method of derivation of geometric manifolds in a dc microgrid that is based on the a-priori computation of the optimal reactions and trajectories for classes of events in a dc microgrid. The proposed states are the stored energies in all the energy storage elements of the dc microgrid and power flowing into them. It is anticipated that calculating a large enough set of dissimilar transient scenarios will also span many scenarios not specifically used to develop the surface. These geometric manifolds will then be used as reference surfaces in any type of controller, such as a sliding mode hysteretic controller. The presence of switched power converters in microgrids involve different control actions for different system events. The control of the switch states of the converters is essential for steady state and transient operations. A digital memory look-up based controller that uses a hysteretic sliding mode control strategy is an effective technique to generate the proper switch states for the converters. An example dcmicrogrid with three dc-dc boost converters and resistive loads is considered for this work. The geometric manifolds are successfully generated for transient events, such as step changes in the loads and the sources. The surfaces corresponding to a specific case of step change in the loads are then used as reference surfaces in an EEPROM for experimentally validating the control strategy. The required switch states corresponding to this specific transient scenario are programmed in the EEPROM as a memory table. This controls the switching of the dc-dc boost converters and drives the system states to the reference manifold. In this work, it is shown that this strategy effectively controls the system for a transient condition such as step changes in the loads for the example case.

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The human immunodeficiency virus-1 reverse transcriptase inhibitory activity of 2-(2,6-disubstituted phenyl)-3-(substituted pyrimidin-2-yl)-thiazolidin-4-ones have been analyzed using combinatorial protocol in multiple linear regression (CP-MLR) with several electronic and molecular surface area features of the compounds obtained from Molecular Operating Environment (MOE) software. The study has indicated the role of different charged molecular surface areas in modeling the inhibitory activity of the compounds. The derived models collectively suggested that the compounds should be compact without bulky substitutions on its peripheries for better HIV-1 RT inhibitory activity. It also emphasized the necessity of hydrophobicity and compact structural features for their activity. The scope of the descriptors identified for these analogues have been verified by extending the dataset with different 2-(disubstituted phenyl)-3-(substituted pyridin-2-yl)-thiazolidin-4-ones. The joint analysis of extended dataset highlighted the information content of identified descriptors in modeling the HIV-1 RT inhibitory activity of the compounds.

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Electrochemical reactivity and structure properties of electrogenic bacteria, Geobacter sulfurreducens (Gs) were studied to explore the heterogeneous electron transfer at the bacteria/electrode interface using electrochemical and in-situ spectroscopic techniques. The redox behavior of Gs adsorbed on a gold electrode, which is modified with a ω-functionalized self-assembled monolayer (SAM) of alkanethiols, depends strongly on the terminal group. The latter interacts directly with outermost cytochromes embedded into the outer membrane of the Gs cells. The redox potential of bacterial cells bound electrostatically to a carboxyl-terminated SAM is close to that observed for bacteria attached to a bare gold electrode, revealing a high electronic coupling at the cell/SAM interface. The redox potentials of bacterial cells adsorbed on amino- and pyridyl-terminated SAMs are significantly different suggesting that the outermost cytochromes changes their conformation upon adsorption on these SAMs. No redox activity of Gs was found with CH3-, N(CH3)3+- and OH-terminated SAMs. Complementary in-situ spectroscopic studies on bacteria/SAMs/Au electrode assemblies were carried out to monitor structure changes of the bacterial cells upon polarization. Spectro-electrochemical techniques revealed the electrochemical turnover of the oxidized and reduced states of outer membrane cytochromes (OMCs) in Gs, providing evidence that the OMCs are responsible for the direct electron transfer to metal electrodes, such as gold or silver, during the electricity production. Furthermore, we observed spectroscopic signatures of the native structure of the OMCs and no conformational change during the oxidation/reduction process of the microorganisms. These findings indicate that the carboxyl-anchoring group provides biocompatible conditions for the outermost cytochromes of the Gs, which facilitate the heterogeneous electron transfer at the microorganism/electrode interface.

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Peatlands deform elastically during precipitation cycles by small (+/- 3 cm) oscillations in surface elevation. In contrast, we used a Global Positioning System network to measure larger oscillations that exceeded 20 cm over periods of 4 - 12 hours during two seasonal droughts at a bog and fen site in northern Minnesota. The second summer drought also triggered 19 depressuring cycles in an overpressured stratum under the bog site. The synchronicity between the largest surface deformations and the depressuring cycles indicates that both phenomena are produced by the episodic release of large volumes of gas from deep semi-elastic compartments confined by dense wood layers. We calculate that the three largest surface deformations were associated with the release of 136 g CH4 m(-2), which exceeds by an order of magnitude the annual average chamber fluxes measured at this site. Ebullition of gas from the deep peat may therefore be a large and previously unrecognized source of radiocarbon depleted methane emissions from northern peatlands.

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The liquid–vapor interface is difficult to access experimentally but is of interest from a theoretical and applied point of view and has particular importance in atmospheric aerosol chemistry. Here we examine the liquid–vapor interface for mixtures of water, sodium chloride, and formic acid, an abundant chemical in the atmosphere. We compare the results of surface tension and X-ray photoelectron spectroscopy (XPS) measurements over a wide range of formic acid concentrations. Surface tension measurements provide a macroscopic characterization of solutions ranging from 0 to 3 M sodium chloride and from 0 to over 0.5 mole fraction formic acid. Sodium chloride was found to be a weak salting out agent for formic acid with surface excess depending only slightly on salt concentration. In situ XPS provides a complementary molecular level description about the liquid–vapor interface. XPS measurements over an experimental probe depth of 51 Å gave the C 1s to O 1s ratio for both total oxygen and oxygen from water. XPS also provides detailed electronic structure information that is inaccessible by surface tension. Density functional theory calculations were performed to understand the observed shift in C 1s binding energies to lower values with increasing formic acid concentration. Part of the experimental −0.2 eV shift can be assigned to the solution composition changing from predominantly monomers of formic acid to a combination of monomers and dimers; however, the lack of an appropriate reference to calibrate the absolute BE scale at high formic acid mole fraction complicates the interpretation. Our data are consistent with surface tension measurements yielding a significantly more surface sensitive measurement than XPS due to the relatively weak propensity of formic acid for the interface. A simple model allowed us to replicate the XPS results under the assumption that the surface excess was contained in the top four angstroms of solution.

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Amawaka ([ɑmɨ̃ˈwɐkɑ]) is a highly endangered and underdocumented tonal language of the Headwaters (Fleck 2011) subgroup of the Panoan family in the Southwest Amazon Basin, spoken by approximately 200 people. Undocumented phonetic and phonological phenomena of Amawaka include its tonal structure, both in terms of surface realizations and the patterns underlying these realizations. Original audiovisual data from the author’s fieldwork in various Amawaka communities at the Peru-Brazil border will illuminate the as-yet obscure tonal systematicity of the language. Unlike other elements, monosyllabic bimoraic phonological nominal words with long vowels display variation in their surface realization. All the words with the open back unrounded /ɑ/, like /ˈkɑ̀:/ (patarashca, a traditional Amazonian dish), /ˈnɑ̀:/ “mestizo” etc. [with the exception of /ˈtɑ:/ “reed”, which surfaces with either a H or L tone] bear a low tone in isolation. This realization contrasts with all the encountered nominal monosyllables with vowels from the close and close-mid front and central spectrum /i, ɘ, ɨ, ɨ̃/, which clearly surface as high tone words in isolation, for example /ˈmɨ̃́:/ (a clay-lick for animals), /ˈwí:/ “Anopheles, spp. mosquito”. Monosyllables with close-mid back rounded /o/ have a less restrictive pitch that varies among speakers from low to high realizations, and sometimes even across the speech tokens from an individual speaker, e.g. /wó:/ or /wō:/ “hair”, /ɧō:/ or /ɧò:/ (a type of tarantula). Phrasal tonal phonology is more complex, when these three kinds of monosyllables appear in larger noun phrases. Some retain the same surface tones as their isolation form, while others seem to vary freely in their surface realization, e.g. /ˈtɘ́:.nɑ̀:/ or /ˈtɘ́:.nɑ́:/ ‘one mestizo’. Yet other monosyllables, e.g. /mɑ̀:/, exhibit a falling tone when preceded by a H syllable, suggesting probably latent tone sandhi phenomena, e.g /ˈtɘ́:.mɑ̂:/ (one clay-lick for parrots). In disyllabic, trisyllabic and quadrisyllabic nouns, tonal and stress patterns generally seem to be more consistent and tend to be retained both in isolation and in larger intonational phrases. Disyllabic nouns, for instance, surface as L-H or L-L when a glottal stop is in coda position. The association of L with a glottal stop is a feature that occurs in other Panoan languages as well, like Capanahua (Loos 1969), and more generally it is an areal feature, found in other parts of Amazonia (Hyman 2010). So, tone has significant interactions with the glottal stop and glottalization, which generally co-occurs with L. The data above suggest that the underlying tonal system of Amawaka is much more complex than the privative one-tone analysis (/H/ vs. Ø, i.e. lack of tone) that was proposed by Russell and Russell (1959). Evidence from field data suggests either an equipollent (Hyman 2010) two-tone opposition between /H/ and /L/, or a hybrid system, with both equipollent and privative features; that is, /H/ vs. /L/ vs. either Ø or /M/. This first systematic description of Amawaka tone, in conjunction with ongoing research, is poised to address broader questions concerning interrelationships between surface/underlying tone and other suprasegmental features, such as nasality, metrical stress, and intonation. References Fleck, David W. 2011. Panoan languages and linguistics. In Javier Ruedas and David W. Fleck (Eds.), Panoan Histories and Interethnic Identities, To appear. Hyman, Larry. 2010. Amazonia and the typology of tone systems. Presented at the conference Amazonicas III: The structure of the Amazonian languages. Bogotá. Loos, Eugene E. 1969. The phonology of Capanahua and its grammatical basis. Norman: SIL and U. Oklahoma. Russell, Robert & Dolores. 1959. Syntactotonemics in Amahuaca (Pano). Série Lingüistica Especial, 128-167. Publicaçoes do Museu Nacional, Rio de Janeiro, Brasil.

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Understanding nuclear and electronic dynamics of molecular systems has advanced considerably by probing their nonlinear responses with a suitable sequence of pulses. Moreover, the ability to control crucial parameters of the excitation pulses, such as duration, sequence, frequency, polarization, slowly varying envelope, or carrier phase, has led to a variety of advanced time-resolved spectroscopic methodologies. Recently, two-dimensional electronic spectroscopy with ultrashort pulses has become a more and more popular tool since it allows to obtain information on energy and coherence transfer phenomena, line broadening mechanisms, or the presence of quantum coherences in molecular complexes. Here, we present a high fidelity two-dimensional electronic spectroscopy setup designed for molecular systems in solution. It incorporates the versatility of pulse-shaping methods to achieve full control on the amplitude and phase of the individual exciting and probing pulses. Selective and precise amplitude- and phase-modulation is shown and applied to investigate electronic dynamics in several reference molecular systems.

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In order to reconstruct Late Quatemary variations of surface oceanography in the eastequatorial South Atlantic, time series of sea-surface temperatures (SST) and paleoproductivity were established from cores recovered in the Guinea and Angola Basins, and at the Walvis Ridge. These records, based on sedimentary alkenone and organic carbon concentrations, reveal that during the last 350,000 years surface circulation and productivity changes in the east-equatorial South Atlantic were highiy sensitive to climate forcing at 23- and 100-kyr periodicities. Covarying SST and paleoproductivity changes at the equator and at the Walvis Ridge appear to be driven by variations in zonal trade-wind intensity, which forces intensification or reduction of coastal and equatorial upwelling, as well as enhanced Benguela cold water advection from the South. Phase relationships of precessional variations in the paleoproductivity and SST records from the distinct sites were evaluated with respect to boreal summer insolation over Africa, movements of southem ocean thermal fronts, and changes in global ice volume. The 23-kyr phasing implies a sensitivity of eastem South Atlantic surface water advection and upwelling to West African monsoon intensity and to changes in the position ofthe subtropical high pressure cell over the South Atlantic, both phenomena which modulate zonal strength of southeasterly trades. SST and productivity changes north of 20°S lack significant variance at the 41-kyr periodicity; and at the Walvis Ridge and the equator lead changes in ice volume. This may indicate that obliquity-driven clirnate change, characteristic for northem high latitudes, e.g fluctuations in continental ice masses, did not substantially influence subtropical and tropical surface circulation in the South Atlantic. At the 23-kyr cycle SST and productivity changes in the eastern Angola Basin lag those in the equatorial Atlantic and at the Walvis Ridge by about 3500 years. This lag is explained by variations in cross-equatorial surface water transport and west-east countercurrent retum flow modifying precessional variations of SST and productivity in the eastem Angola Basin relative to those in the mid South Atlantic area under the central field of zonal trade winds. Sea level-related shifts of upwelling cells in phase with global clirnate change may be also recorded in SST and productivity variability along the continental margin off Southwest Africa. They may account for the delay of the paleoceanogreaphic signal from continental margin sites with respect to that from the pelagic sites at the equator and the Walvis Ridge.

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B/Ca ratios in Cibicides mundulus and Cibicides wuellerstorfi have been shown to correlate with the degree of calcite saturation in seawater (D[CO32-]). In the South Pacific, a region of high importance in the global carbon cycle, these species are not continuously present in down-core records. Small numbers of epibenthic foraminifera in samples present an additional challenge, which can be overcome by using laser ablation-inductively coupled-mass spectrometry (LA-ICP-MS). We present a laser ablation based core-top calibration for Cibicides cf. wuellerstorfi, a C. wuellerstorfi morphotype that is abundant in the South Pacific and extend the existing global core top calibration for C. mundulus and C. wuellerstorfi to this region. B/Ca in C. cf. wuellerstorfi are linearly correlated with D[CO32-] and possibly display a higher sensitivity to calcite saturation changes than C. wuellerstorfi. Trace element profiles through C. wuellerstorfi and C. mundulus reveal an intra-shell B/Ca variation of ±36% around the mean shell value. Mg/Ca and B/Ca display opposite trends along the shell. Both phenomena likely result from ontogenetic effects. Intra-shell variability equals intra-sample variability, mean sample B/Ca values can thus be reliably calculated from averaged spot results of single specimen. In the global B/Ca-D[CO32-] range, we observe an inverse relationship between water mass age and D[CO32-].