Electron energy loss spectroscopy: physical principles, state of the art and applications to the nanosciences

In the present work we review the way in which the electron-matter interaction allows us to perform electron energy loss spectroscopy (EELS), as well as the latest developments in the technique and some of the most relevant results of EELS as a characterization tool in nanoscience and nanotechnology.

Electron probe microanalysis: principles and applications

This article summarizes the basic principles of electron probe microanalysis, with examples of applications in materials science and geology that illustrate the capabilities of the technique.

Long-lived States in an intrinsically disordered protein domain

Long-lived states (LLS) are relaxation-favoured eigenstates of J-coupled magnetic nuclei. LLS were measured, along with classical 1H and 15 N relaxation rate constants, in aminoacids of the N-terminal Unique domain of the c-Src kinase (USrc), which is disordered in vitro under physiological conditions. The relaxation rates of LLS are a probe for motions and interactions in biomolecules. LLS of the aliphatic protons of glycines, with lifetimes ca. four times longer than their spin-lattice relaxation times, are reported for the first time in an intrinsically disordered protein domain (IDP). LLS relaxation experiments were integrated with 2D spectroscopy methods, further adapting them for studies on proteins.

Blue luminescence at room temperature in defective MgO films

Luminescence spectroscopy has been used to characterize MgO films prepared by rf-sputtering. A clear correlation is found between the appearance of an emission peak centered at approximately 460 nm and the detection of ferromagnetic ordering in the samples. We suggest that cationic vacancies are responsible for the blue-light emission by introducing p states into the electronic band-gap. In accordance with this, our results strongly indicate that cationic vacancies are at the heart of the appearance of long-range magnetic ordering in MgO films.

Microwave spectrometry for the Evaluation of the structural integrity of metallic stents

Purpose: To assess the feasibility of a method based on microwave spectrometry to detect structural distortions of metallic stents in open air conditions and envisage the prospects of this approach toward possible medical applicability for the evaluation of implanted stents. Methods: Microwave absorbance spectra between 2.0 and 18.0 GHz were acquired in open air for the characterization of a set of commercial stents using a specifically design setup. Rotating each sample over 360º, 2D absorbance diagrams were generated as a function of frequency and rotation angle. To check our approach for detecting changes in stent length (fracture) and diameter (recoil), two specific tests were performed in open air. Finally, with a few adjustments, this same system provides 2D absorbance diagrams of stents immersed in a water-based phantom, this time over a bandwidth ranging from 0.2 to 1.8 GHz. Results: The authors show that metallic stents exhibit characteristic resonant frequencies in their microwave absorbance spectra in open air which depend on their length and, as a result, may reflect the occurrence of structural distortions. These resonances can be understood considering that such devices behave like dipole antennas in terms of microwave scattering. From fracture tests, the authors infer that microwave spectrometry provides signs of presence of Type I to Type IV stent fractures and allows in particular a quantitative evaluation of Type III and Type IV fractures. Recoil tests show that microwave spectrometry seems able to provide some quantitative assessment of diametrical shrinkage, but only if it involves longitudinal shortening. Finally, the authors observe that the resonant frequencies of stents placed inside the phantom shift down with respect to the corresponding open air frequencies, as it should be expected considering the increase of dielectric permittivity from air to water. Conclusions: The evaluation of stent resonant frequencies provided by microwave spectrometry allows detection and some quantitative assessment of stent fracture and recoil in open air conditions. Resonances of stents immersed in water can be also detected and their characteristic frequencies are in good agreement with theoretical estimates. Although these are promising results, further verifica tion in a more relevant phantom is required in order to foresee the real potential of this approach.

Identification of neuronal network properties from the spectral analysis of calcium imaging signals in neuronal cultures

Neuronal networks in vitro are prominent systems to study the development of connections in living neuronal networks and the interplay between connectivity, activity and function. These cultured networks show a rich spontaneous activity that evolves concurrently with the connectivity of the underlying network. In this work we monitor the development of neuronal cultures, and record their activity using calcium fluorescence imaging. We use spectral analysis to characterize global dynamical and structural traits of the neuronal cultures. We first observe that the power spectrum can be used as a signature of the state of the network, for instance when inhibition is active or silent, as well as a measure of the network's connectivity strength. Second, the power spectrum identifies prominent developmental changes in the network such as GABAA switch. And third, the analysis of the spatial distribution of the spectral density, in experiments with a controlled disintegration of the network through CNQX, an AMPA-glutamate receptor antagonist in excitatory neurons, reveals the existence of communities of strongly connected, highly active neurons that display synchronous oscillations. Our work illustrates the interest of spectral analysis for the study of in vitro networks, and its potential use as a network-state indicator, for instance to compare healthy and diseased neuronal networks.

Quasi real-time Raman studies on the growth of Cu-In-S thin films

In this work annealing and growth of CuInS2 thin films is investigated with quasireal-time in situ Raman spectroscopy. During the annealing a shift of the Raman A1 mode towards lower wave numbers with increasing temperature is observed. A linear temperature dependence of the phonon branch of ¿2 cm¿1/100 K is evaluated. The investigation of the growth process (sulfurization of metallic precursors) with high surface sensitivity reveals the occurrence of phases which are not detected with bulk sensitive methods. This allows a detailed insight in the formation of the CuInS2 phases. Independent from stoichiometry and doping of the starting precursors the CuAu ordering of CuInS2 initially forms as the dominating ordering. The transformation of the CuAu ordering into the chalcopyrite one is, in contrast, strongly dependent on the precursor composition and requires high temperatures.

Diradicals acting through diamagnetic phenylene vinylene bridges: Raman spectroscopy as a probe to characterize spin delocalization

We present a complete Raman spectroscopic study in two structurally well-defined diradical species of different lengths incorporating oligo p-phenylene vinylene bridges between two polychlorinated triphenylmethyl radical units, a disposition that allows sizeable conjugation between the two radicals through and with the bridge. The spectroscopic data are interpreted and supported by quantum chemical calculations. We focus the attention on the Raman frequency changes, interpretable in terms of: (i) bridge length (conjugation length); (ii) bridge conformational structure; and (iii) electronic coupling between the terminal radical units with the bridge and through the bridge, which could delineate through-bond spin polarization, or spin delocalization. These items are addressed by using the"oligomer approach" in conjunction with pressure and temperature dependent Raman spectroscopic data. In summary, we have attempted to translate the well-known strategy to study the electron (charge) structure of π−conjugated molecules by Raman spectroscopy to the case of electron (spin) interactions via the spin delocalization mechanism.

Aplicación de la técnica de espectrometría de fluorescencia de rayos-X en el estudio de la dispersión de metales en áreas mineras

One critical factor for success in characterizing metals polluting mining environments so as to be able to eliminate them and subsequently recover these areas depends upon a speedy and correct response in the analysis of samples. Rapid, simultaneous, multi-element analysis can be undertaken using X-ray fluorescence spectrometry, a versatile, non-destructive analytical technique commonly employed to identify both major and minor elements in samples related to environmental studies. An additional advantage of this technique is the possibility of conducting the analysis directly on solid samples, which is extremely convenient when dealing with environmental samples that are difficult to dissolve, such as soils, sediments and mining wastes. Moreover, in recent years the development of spectrometers equipped with digital-signal processors combined with enlarged X-ray production, using better designs for excitation-detection, has contributed to an improvement in instrumental sensitivity, thus allowing us to detect important polluting elements such as Cd and Pb at trace levels. In this paper the authors describe, on the basis of their own experience, some interesting applications of XRF spectrometry for the analysis of several types of environmental samples related to the study of the dispersion of metals within mining environments: (A) analysis of mining wastes, soils and sediments; (B) analysis of samples of vegetation used as bioindicators or related to phytoremediation studies; and (C) analysis of water samples related to mining operations

Prediction of crude protein and classification of the growth stage of wheat plant samples from NIR spectra

Near-infrared spectroscopy (NIRS) was used to analyse the crude protein content of dried and milled samples of wheat and to discriminate samples according to their stage of growth. A calibration set of 72 samples from three growth stages of wheat (tillering, heading and harvest) and a validation set of 28 samples was collected for this purpose. Principal components analysis (PCA) of the calibration set discriminated groups of samples according to the growth stage of the wheat. Based on these differences, a classification procedure (SIMCA) showed a very accurate classification of the validation set samples : all of them were successfully classified in each group using this procedure when both the residual and the leverage were used in the classification criteria. Looking only at the residuals all the samples were also correctly classified except one of tillering stage that was assigned to both tillering and heading stages. Finally, the determination of the crude protein content of these samples was considered in two ways: building up a global model for all the growth stages, and building up local models for each stage, separately. The best prediction results for crude protein were obtained using a global model for samples in the two first growth stages (tillering and heading), and using a local model for the harvest stage samples.

A Be-type star with a black-hole companion

Stellar-mass black holes have all been discovered through X-ray emission, which arises from the accretion of gas from their binary companions (this gas is either stripped from low-mass stars or supplied as winds from massive ones). Binary evolution models also predict the existence of black holes accreting from the equatorial envelope of rapidly spinning Be-type stars (stars of the Be type are hot blue irregular variables showing characteristic spectral emission lines of hydrogen). Of the ~80 Be X-ray binaries known in the Galaxy, however, only pulsating neutron stars have been found as companions. A black hole was formally allowed as a solution for the companion to the Be star MWC 656 (also known as HD 215227), although that was based on a single radial velocity curve of the Be star, a mistaken spectral classification and rough estimates of the inclination angle. Here we report observations of an accretion disk line mirroring the orbit of the Be star. This, together with an improved radial velocity curve of the Be star through fitting sharp Fe II profiles from the equatorial disk, and a refined Be classification (to that of a B1.5-B2 III star), reveals a black hole of 3.8 to 6.9 solar masses orbiting MWC 656, the candidate counterpart of the gamma-ray source AGL J2241+4454. The black hole is X-ray quiescent and fed by a radiatively inefficient accretion flow giving a luminosity less than 1.6 x 10-7 times the Eddington luminosity. This implies that Be binaries with black-hole companions are difficult to detect by conventional X-ray surveys.

Spectral analysis of the angular distribution function of back reflectors for thin film silicon solar cells

Nowadays, one of the most important challenges to enhance the efficiency of thin film silicon solar cells is to increase the short circuit intensity by means of optical confinement methods, such as textured back-reflector structures. In this work, two possible textured structures to be used as back reflectors for n-i-p solar cells have been optically analyzed and compared to a smooth one by using a system which is able to measure the angular distribution function (ADF) of the scattered light in a wide spectral range (350-1000 nm). The accurate analysis of the ADF data corresponding to the reflector structures and to the μc-Si:H films deposited onto them allows the optical losses due to the reflector absorption and its effectiveness in increasing light absorption in the μc-Si:H layer, mainly at long wavelengths, to be quantified.

Relaxation and derelaxation of pure and hydrogenated amorphous silicon during thermal annealing experiments

The structural relaxation of pure amorphous silicon a-Si and hydrogenated amorphous silicon a-Si:H materials, that occurs during thermal annealing experiments, has been analyzed by Raman spectroscopy and differential scanning calorimetry. Unlike a-Si, the heat evolved from a-Si:H cannot be explained by relaxation of the Si-Si network strain but it reveals a derelaxation of the bond angle strain. Since the state of relaxation after annealing is very similar for pure and hydrogenated materials, our results give strong experimental support to the predicted configurational gap between a-Si and crystalline silicon.

Identification of neuronal network properties from the spectral analysis of calcium imaging signals in neuronal cultures

Neuronal networks in vitro are prominent systems to study the development of connections in living neuronal networks and the interplay between connectivity, activity and function. These cultured networks show a rich spontaneous activity that evolves concurrently with the connectivity of the underlying network. In this work we monitor the development of neuronal cultures, and record their activity using calcium fluorescence imaging. We use spectral analysis to characterize global dynamical and structural traits of the neuronal cultures. We first observe that the power spectrum can be used as a signature of the state of the network, for instance when inhibition is active or silent, as well as a measure of the network's connectivity strength. Second, the power spectrum identifies prominent developmental changes in the network such as GABAA switch. And third, the analysis of the spatial distribution of the spectral density, in experiments with a controlled disintegration of the network through CNQX, an AMPA-glutamate receptor antagonist in excitatory neurons, reveals the existence of communities of strongly connected, highly active neurons that display synchronous oscillations. Our work illustrates the interest of spectral analysis for the study of in vitro networks, and its potential use as a network-state indicator, for instance to compare healthy and diseased neuronal networks.