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We report on the direct correlation between the structural and optical properties of single, as-grown core-multi-shell GaAs/In0.15Ga0.85As/GaAs/AlAs/GaAs nanowires. Fabricated by molecular beam epitaxy on a pre-patterned Si(111) substrate, on a row of well separated nucleation sites, it was possible to access individual nanowires in the as-grown geometry. The polytype distribution along the growth axis of the nanowires was revealed by synchrotron-based nanoprobe x-ray diffraction techniques monitoring the axial 111 Bragg reflection. For the same nanowires, the spatially-resolved emission properties were obtained by cathodoluminescence hyperspectral linescans in a scanning electron microscope. Correlating both measurements, we reveal a blueshift of the shell quantum well emission energy combined with an increased emission intensity for segments exhibiting a mixed structure of alternating wurtzite and zincblende stacking compared with the pure crystal polytypes. The presence of this mixed structure was independently confirmed by cross-sectional transmission electron microscopy.
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We present and demonstrate a formalism by which three-dimensional (3D) Bragg x-ray coherent diffraction imaging (BCDI) can be implemented without moving the sample by scanning the energy of the incident x-ray beam. This capability is made possible by introducing a 3D Fourier transform that accounts for x-ray wavelength variability. We demonstrate the approach by inverting coherent Bragg diffraction patterns from a gold nanocrystal measured with an x-ray energy scan. Variable-wavelength BCDI will expand the breadth of feasible in situ 3D strain imaging experiments towards more diverse materials environments, especially where sample manipulation is difficult.
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The Materials Science beamline at the Swiss Light Source has been operational since 2001. In late 2010, the original wiggler source was replaced with a novel insertion device, which allows unprecedented access to high photon energies from an undulator installed in a medium-energy storage ring. In order to best exploit the increased brilliance of this new source, the entire front-end and optics had to be redesigned. In this work, the upgrade of the beamline is described in detail. The tone is didactic, from which it is hoped the reader can adapt the concepts and ideas to his or her needs.
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Electronic or catalytic properties can be modified at the nanoscale level. Engineering efficient and specific nanomaterials requires the ability to study their complex structure-property relationships. Here, Bragg coherent diffraction imaging was used to measure the three-dimensional shape and strain of platinum nanoparticles with a diameter smaller than 30â nm, i.e. significantly smaller than any previous study. This was made possible by the realization of the Extremely Brilliant Source of ESRF, The European Synchrotron. This work demonstrates the feasibility of imaging the complex structure of very small particles in three dimensions and paves the way towards the observation of realistic catalytic particles.
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The evolution of the atomic structure of LaAlO_{3} grown on SrTiO_{3} was investigated using surface x-ray diffraction in conjunction with model-independent, phase-retrieval algorithms between two and five monolayers film thickness. A depolarizing buckling is observed between cation and oxygen positions in response to the electric field of polar LaAlO_{3}, which decreases with increasing film thickness. We explain this in terms of competition between elastic strain energy, electrostatic energy, and electronic reconstructions. Based on these structures, the threshold for formation of a two-dimensional electron system at a film thickness of 4 monolayers is quantitatively explained. The findings are also qualitatively reproduced by density-functional-theory calculations.
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Alumínio/química , Lantânio/química , Óxidos/química , Estrôncio/química , Titânio/química , Difração de Raios XRESUMO
We present a direct comparison between experimental data and ab initio calculations for the electrostrictive effect in the polar LaAlO(3) layer grown on SrTiO(3) substrates. From the structural data, a complete screening of the LaAlO(3) dipole field is observed for film thicknesses between 6 and 20 uc. For thinner films, an expansion of the c axis of 2% matching the theoretical predictions for an electrostrictive effect is observed experimentally.
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BACKGROUND: Skin ageing is said to be caused by multiple factors. The relationship with sun exposure is of particular interest because the detrimental cutaneous effects of the sun may be a strong motivator to sun protection. We report a study of skin ageing in participants of an epidemiological study of melanoma. OBJECTIVES: To determine the predictors of periorbital cutaneous ageing and whether it could be used as an objective marker of sun exposure. METHODS: Photographs of the periorbital skin in 1341 participants were graded for wrinkles, degree of vascularity and blotchy pigmentation and the resultant data assessed in relation to reported sun exposure, sunscreen use, body mass index (BMI), smoking and the melanocortin 1 receptor (MC1R) gene status. Data were analysed using proportional odds regression. RESULTS: Wrinkling was associated with age and heavy smoking. Use of higher sun-protection factor sunscreen was protective (P = 0·01). Age, male sex, MC1R variants ('r', P=0·01; 'R', P=0·02), higher reported daily sun exposure (P=0·02), increased BMI (P=0·01) and smoking (P=0·02) were risk factors for hypervascularity. Blotchy pigmentation was associated with age, male sex, higher education and higher weekday sun exposure (P=0·03). More frequent sunscreen use (P=0·02) and MC1R variants ('r', P=0·03; 'R', P=0·001) were protective. CONCLUSIONS: Periorbital wrinkling is a poor biomarker of reported sun exposure. Vascularity is a better biomarker as is blotchy pigmentation, the latter in darker-skinned individuals. In summary, male sex, sun exposure, smoking, obesity and MC1R variants were associated with measures of cutaneous ageing. Sunscreen use showed some evidence of being protective.
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Melanoma/patologia , Envelhecimento da Pele/efeitos da radiação , Neoplasias Cutâneas/patologia , Luz Solar/efeitos adversos , Adulto , Idoso , Estudos de Casos e Controles , Feminino , Genótipo , Humanos , Masculino , Pessoa de Meia-Idade , Obesidade/complicações , Obesidade/patologia , Variações Dependentes do Observador , Órbita , Receptor Tipo 1 de Melanocortina/genética , Pele/irrigação sanguínea , Envelhecimento da Pele/genética , Pigmentação da Pele , Fumar/efeitos adversos , Queimadura Solar/patologiaRESUMO
A reactor cell for in situ studies of individual catalyst nanoparticles or surfaces by nano-focused (coherent) x-ray diffraction has been developed. Catalytic reactions can be studied in flow mode in a pressure range of 10-2-103 mbar and temperatures up to 900 °C. This instrument bridges the pressure and materials gap at the same time within one experimental setup. It allows us to probe in situ the structure (e.g., shape, size, strain, faceting, composition, and defects) of individual nanoparticles using a nano-focused x-ray beam. Here, the setup was used to observe strain and facet evolution of individual model Pt catalysts during in situ experiments. It can be used for heating other (non-catalytically active) nanoparticles (e.g., nanowires) in inert or reactive gas atmospheres or vacuum as well.
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Simulating groundwater flow in basin-fill aquifers of the semiarid southwestern United States commonly requires decisions about how to distribute aquifer recharge. Precipitation can recharge basin-fill aquifers by direct infiltration and transport through faults and fractures in the high-elevation areas, by flowing overland through high-elevation areas to infiltrate at basin-fill margins along mountain fronts, by flowing overland to infiltrate along ephemeral channels that often traverse basins in the area, or by some combination of these processes. The importance of accurately simulating recharge distributions is a current topic of discussion among hydrologists and water managers in the region, but no comparative study has been performed to analyze the effects of different recharge distributions on groundwater simulations. This study investigates the importance of the distribution of aquifer recharge in simulating regional groundwater flow in basin-fill aquifers by calibrating a groundwater-flow model to four different recharge distributions, all with the same total amount of recharge. Similarities are seen in results from steady-state models for optimized hydraulic conductivity values, fit of simulated to observed hydraulic heads, and composite scaled sensitivities of conductivity parameter zones. Transient simulations with hypothetical storage properties and pumping rates produce similar capture rates and storage change results, but differences are noted in the rate of drawdown at some well locations owing to the differences in optimized hydraulic conductivity. Depending on whether the purpose of the groundwater model is to simulate changes in groundwater levels or changes in storage and capture, the distribution of aquifer recharge may or may not be of primary importance.
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Água Subterrânea , Hidrologia , Modelos Teóricos , Chuva , Sudoeste dos Estados Unidos , Movimentos da ÁguaRESUMO
Raw milk samples collected from bulk milk tankers may be screened for the presence of tetracycline antibiotics using rapid screening tests. If tetracycline residues are detected, the milk may be shipped to a laboratory for high-pressure liquid chromatography (HPLC) analysis. Because the milk may be shipped on ice blocks, it is important to know whether tetracycline residues are stable at that temperature and for how long. Control raw milk samples fortified with 50 ppb each chlortetracycline, demeclocycline, methacycline hydrochloride, minocycline, oxytetracycline, and tetracycline were incubated at 4 degrees C or 25 degrees C, then analyzed using a metal chelate affinity chromatography extraction and HPLC. No loss of tetracycline was observed after 48 h of storage at 4 degrees C or 24 h at 25 degrees C. Losses ranging from 4 to 13% and 0 to 18% were noted after 72 h at 4 degrees C and 48 h at 25 degrees C, respectively.
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Antibacterianos/análise , Resíduos de Drogas/análise , Manipulação de Alimentos , Leite/química , Animais , Antibacterianos/química , Cromatografia Líquida de Alta Pressão , Resíduos de Drogas/química , Estabilidade de Medicamentos , Padrões de Referência , Temperatura , TetraciclinasRESUMO
A natural consequence of groundwater withdrawals is the removal of water from subsurface storage, but the overall rates and magnitude of groundwater depletion and capture relative to groundwater withdrawals (extraction or pumpage) have not previously been well characterized. This study assesses the partitioning of long-term cumulative withdrawal volumes into fractions derived from storage depletion and capture, where capture includes both increases in recharge and decreases in discharge. Numerical simulation of a hypothetical groundwater basin is used to further illustrate some of Theis' (1940) principles, particularly when capture is constrained by insufficient available water. Most prior studies of depletion and capture have assumed that capture is unconstrained through boundary conditions that yield linear responses. Examination of real systems indicates that capture and depletion fractions are highly variable in time and space. For a large sample of long-developed groundwater systems, the depletion fraction averages about 0.15 and the capture fraction averages about 0.85 based on cumulative volumes. Higher depletion fractions tend to occur in more arid regions, but the variation is high and the correlation coefficient between average annual precipitation and depletion fraction for individual systems is only 0.40. Because 85% of long-term pumpage is derived from capture in these real systems, capture must be recognized as a critical factor in assessing water budgets, groundwater storage depletion, and sustainability of groundwater development. Most capture translates into streamflow depletion, so it can detrimentally impact ecosystems.
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Monitoramento Ambiental , Água Subterrânea/análise , Abastecimento de Água/análise , Conservação dos Recursos Naturais , Poços de Água/análiseRESUMO
The properties of single-crystal SrTiO3 substrates and homoepitaxial SrTiO3 films grown by pulsed laser deposition have been compared, in order to understand the loss of interfacial conductivity when more than a critical thickness of nominally homoepitaxial SrTiO3 is inserted between a LaAlO3 film and a SrTiO3 substrate. In particular, the chemical composition and the structure of homoepitaxial SrTiO3 investigated by low-energy ion-scattering and surface X-ray diffraction show that for insulating heterointerfaces, a Sr-excess is present between the LaAlO3 and homoepitaxial SrTiO3. Furthermore, an increase in the out-of-plane lattice constant is observed in LaAlO3, indicating that the conductivity both with and without insertion of the SrTiO3 thin film originates from a Zener breakdown associated with the polar catastrophe. When more than a critical thickness of homoepitaxial SrTiO3 is inserted between LaAlO3 and SrTiO3, the electrons transferred by the electronic reconstruction are trapped by the formation of a Sr-rich secondary phase and Sr-vacancies. The migration of Sr towards the surface of homoepitaxial SrTiO3 and accompanying loss of interfacial conductivity can be delayed by reducing the Sr-content in the PLD target.
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The application of multi-wavelength anomalous diffraction to thin films, interfaces and surface structures is presented. The method directly determines the amplitudes and phases of the complex surface structure factors from surface x-ray diffraction data, measured at three different energies around the absorption edge of one of the elements present in the film. Thereby, one is able to directly Fourier transform the data, which immediately provides meaningful and unambiguous electron-density distributions. These serve as a starting point for subsequent structural refinement. The robustness of the algorithm was evaluated on simulated data as a proof of principle. The experimental limitations and their effect on the method will be discussed as well as stability tests for the algorithm, such as the positions of the anomalous scatterers and the interfacial roughness. It will be shown that the method can be applied to real structures. The algorithm was tested on real data from a thin film of SrTiO(3) grown on NdGaO(3)(110).