Sulfur K-edge x-ray absorption spectroscopy: A spectroscopic tool to examine the redox state of S-containing metabolites in vivo

The sulfur K-edge x-ray absorption spectra for the amino acids cysteine and methionine and their corresponding oxidized forms cystine and methionine sulfoxide are presented. Distinct differences in the shape of the edge and the inflection point energy for cysteine and cystine are observed. For methionine sulfoxide the inflection point energy is 2.8 eV higher compared with methionine. Glutathione, the most abundant thiol in animal cells, also has been investigated. The x-ray absorption near-edge structure spectrum of reduced glutathione resembles that of cysteine, whereas the spectrum of oxidized glutathione resembles that of cystine. The characteristic differences between the thiol and disulfide spectra enable one to determine the redox status (thiol to disulfide ratio) in intact biological systems, such as unbroken cells, where glutathione and cyst(e)ine are the two major sulfur-containing components. The sulfur K-edge spectra for whole human blood, plasma, and erythrocytes are shown. The erythrocyte sulfur K-edge spectrum is similar to that of fully reduced glutathione. Simulation of the plasma spectrum indicated 32% thiol and 68% disulfide sulfur. The whole blood spectrum can be simulated by a combination of 46% disulfide and 54% thiol sulfur.

The application of X-ray photoelectron spectroscopy to clay science

Photo-electron spectroscopy as an analytical tool has only received limited interest in the field of mineral science. Photo-electron spectroscopy, together with Auger electron spectroscopy, gives information about the positions of the energy levels in atoms or molecules. Application of this technique on solid materials will result in information of the band structure of these materials. The principle of photo electron spectroscopy is rather simple: photons with certain energy (wavelength) are allowed to collide with an atom, molecule or a solid material. These photons can then interact with electrons present in the atoms and one of these electrons can be excited from its orbital resulting in a situation similar to a free electron plus a positively charged atom or molecule.

Fast x-ray spectroscopy study of ethene on clean and SO4 precovered Pt{111}

The adsorption and decomposition of ethylene over a Pt{111} single crystalsurface has been investigated by fast x-ray spectroscopy. At 100 K ethene displays precursor-mediated adsorption kinetics, adopting a single environment with a saturation C2H4 coverage of 0.25 ML and binding energy of 283.2 eV. Thermal decomposition proceeds above 240 K via dehydrogenation to ethylidyne with an activation barrier of 57±3 kJ mol−1 and preexponential factor ν=1×1010±0.5 s−1. Site-blocking by preadsorbed SO4 reduces the saturation ethene coverage but induces a new, less reactive π-bonded ethene species centered around 283.9 eV, which in turn decomposes to ethylidyne at 350 K.

X-Ray Absorption Spectroscopy and Computer Modelling Study of Nanocrystalline Binary Alkaline Earth Fluorides

Nanocrystalline samples of Ba1-xCaxF2 prepared by high-energy milling show an unusually high F-ion conductivity, which exhibit a maximum in the magnitude and a minimum in the activation energy at x = 0.5. Here, we report an X-ray absorption spectroscopy (XAS) at the Ca and Sr K edges and the Ba L-3 edge and a molecular dynamics (MD) simulation study of the pure and mixed fluorides. The XAS measurements on the pure binary fluorides, CaF2, SrF2 and BaF2 show that high-energy ball-milling produces very little amorphous material, in contrast to the results for ball milled oxides. XAS measurements of Ba1-xCaxF2 reveal that for 0 < x < 1 there is considerable disorder in the local environments of the cations which is highest for x = 0.5. Hence the maximum in the conductivity corresponds to the composition with the maximum level of local disorder. The MD calculations also show a highly disordered structure consistent with the XAS results and similarly showing maximum disorder at x = 0.5.

Cluster and cluster galaxy evolution history from IR to X-ray observations of the young cluster RX J1257.2+4738 at z=0.866

Context. The cosmic time around the z similar to 1 redshift range appears crucial in the cluster and galaxy evolution, since it is probably the epoch of the first mature galaxy clusters. Our knowledge of the properties of the galaxy populations in these clusters is limited because only a handful of z similar to 1 clusters are presently known. Aims. In this framework, we report the discovery of a z similar to 0.87 cluster and study its properties at various wavelengths. Methods. We gathered X-ray and optical data (imaging and spectroscopy), and near and far infrared data (imaging) in order to confirm the cluster nature of our candidate, to determine its dynamical state, and to give insight on its galaxy population evolution. Results. Our candidate structure appears to be a massive z similar to 0.87 dynamically young cluster with an atypically high X-ray temperature as compared to its X-ray luminosity. It exhibits a significant percentage (similar to 90%) of galaxies that are also detected in the 24 mu m band. Conclusions. The cluster RXJ1257.2+4738 appears to be still in the process of collapsing. Its relatively high temperature is probably the consequence of significant energy input into the intracluster medium besides the regular gravitational infall contribution. A significant part of its galaxies are red objects that are probably dusty with on-going star formation.

Synchrotron X-ray powder diffraction and extended X-ray absorption fine structure spectroscopy studies on nanocrystalline ZrO(2)-CaO solid solutions

The crystal structure and the local atomic order of a series of nanocrystalline ZrO(2)-CaO solid solutions with varying CaO content were studied by synchrotron radiation X-ray powder diffraction and extended X-ray absorption fine structure (EXAFS) spectroscopy. These samples were synthesized by a pH-controlled nitrate-glycine gel-combustion process. For CaO contents up to 8 mol%, the t' form of the tetragonal phase (c/a > 1) was identified, whereas for 10 and 12 mol% CaO, the t '' form (c/a=1; oxygen anions displaced from their ideal positions in the cubic phase) was detected. Finally, the cubic phase was observed for solid solutions with CaO content of 14 mol% CaO or higher. The t'/t '' and t ''/cubic compositional boundaries were determined to be at 9 (1) and 13 (1) mol% CaO, respectively. The EXAFS study demonstrated that this transition is related to a tetragonal-to-cubic symmetry change of the first oxygen coordination shell around the Zr atoms.

Depth-dependent local structures in thin films unraveled by grazing-incidence X-ray absorption spectroscopy

A method of using X-ray absorption spectroscopy together with resolved grazing-incidence geometry for depth profiling of atomic, electronic or chemical local structures in thin films is presented. The quantitative deconvolution of thickness-dependent spectral features is performed by fully considering both scattering and absorption formalisms. Surface oxidation and local structural depth profiles in nanometric FePt films are determined, exemplifying the application of the method.

gamma Cassiopeiae: an X-ray Be star with personality

An exciting unsolved problem in the study of high energy processes of early type stars concerns the physical mechanism for producing X-rays near the Be star gamma Cassiopeiae. By now we know that this source and several ""gamma Cas analogs"" exhibit an unusual hard thermal X-ray spectrum, compared both to normal massive stars and the non-thermal emission of known Be/X-ray binaries. Also, its light curve is variable on almost all conceivable timescales. In this study we reanalyze a high dispersion spectrum obtained by Chandra in 2001 and combine it with the analysis of a new (2004) spectrum and light curve obtained by XMM-Newton. We find that both spectra can be fit well with 3-4 optically thin, thermal components consisting of a hot component having a temperature kT(Q) similar to 12-14 keV, perhaps one with a value of similar to 2.4 keV, and two with well defined values near 0.6 keV and 0.11 keV. We argue that these components arise in discrete (almost monothermal) plasmas. Moreover, they cannot be produced within an integral gas structure or by the cooling of a dominant hot process. Consistent with earlier findings, we also find that the Fe abundance arising from K-shell ions is significantly subsolar and less than the Fe abundance from L-shell ions. We also find novel properties not present in the earlier Chandra spectrum, including a dramatic decrease in the local photoelectric absorption of soft X-rays, a decrease in the strength of the Fe and possibly of the Si K fluorescence features, underpredicted lines in two ions each of Ne and N (suggesting abundances that are similar to 1.5-3x and similar to 4x solar, respectively), and broadening of the strong NeXLy alpha and OVIII Ly alpha lines. In addition, we note certain traits in the gamma Cas spectrum that are different from those of the fairly well studied analog HD110432 - in this sense the stars have different ""personalities."" In particular, for gamma Cas the hot X-ray component remains nearly constant in temperature, and the photoelectric absorption of the X-ray plasmas can change dramatically. As found by previous investigators of gamma Cas, changes in flux, whether occurring slowly or in rapidly evolving flares, are only seldomly accompanied by variations in hardness. Moreover, the light curve can show a ""periodicity"" that is due to the presence of flux minima that recur semiregularly over a few hours, and which can appear again at different epochs.

Synthesis of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2), a hydroxo-bridged copper(II) complex of N,N '-dimethyl-1-thia-4,7-diazacyclononane (Me-2[9]aneN(2)S). X-ray structural analysis, magnetic susceptibility, EPR and visible spectroscopy

The bis(mu-hydroxo) complex [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)](PF6)(2) (Me-2[9]aneN(2)S = N,N'-dimethyl-1-thia-4,7-diazacyclononane) results after reaction of [Cu(Me-2[9]aneN(2)S)(MeCN)] (PF6) with dioxygen at -78 degrees C in acetonitrile. The complex has been characterized by X-ray crystallography: orthorhombic, space group Pnma, with a 18.710(3), b 16.758(2), c 9.593(2) Angstrom, and Z = 4. The structure refined to a final R value of 0.051. The complex contains two copper(II) ions bridged by two hydroxo groups with Cu ... Cu 2.866(1) Angstrom. The solid-state magnetic susceptibility study reveals ferromagnetic coupling, the fitting parameters being J = +46+/-5 cm(-1), g = 2.01+/-0.01 and theta = -0.58+/-0.03 K. The frozen-solution e.p.r. spectrum in dimethyl sulfoxide is characteristic of a monomeric copper(II) ion (g(parallel to) 2.300, g(perpendicular to) 2.063; A(parallel to) 156.2 x 10(-4) cm(-1), A(perpendicular to) 9.0 x 10(-4) cm(-1)) with an N2O2 donor set. Thioether coordination to the copper(II) in solution is supported by the presence of an intense absorption assigned to a sigma(S)-->Cu-II LMCT transition at c. 34000 cm(-1). The single-crystal spectrum of [Cu-2(Me-2[9]aneN(2)S)(2)(OH)(2)] (PF6)(2) (273 K) reveals d-->d transitions at 14500 and 18300 cm(-1) and a weak pi(S)-->Cu-II charge-transfer band at approximately 25000 cm(-1).

Assessment of limb muscle and adipose tissue by dual-energy X-ray absorptiometry using magnetic resonance imaging for comparison

OBJECTIVE: To use magnetic resonance imaging (MRI) to validate estimates of muscle and adipose tissue (AT) in lower limb sections obtained by dual-energy X-ray absorptiometry (DXA) modelling. DESIGN: MRI measurements were used as reference for validating limb muscle and AT estimates obtained by DXA models that assume fat-free soft tissue (FFST) comprised mainly muscle: model A accounted for bone hydration only; model B also applied constants for FFST in bone and skin and fat in muscle and AT; model C was as model B but allowing for variable fat in muscle and AT. SUBJECTS: Healthy men (n = 8) and women (n = 8), ages 41 - 62 y; mean (s.d.) body mass indices (BMIs) of 28.6 (5.4) kg/m(2) and 25.1 (5.4) kg/m2, respectively. MEASUREMENTS: MRI scans of the legs and whole body DXA scans were analysed for muscle and AT content of thigh (20 cm) and lower leg (10 cm) sections; 24 h creatinine excretion was measured. RESULTS: Model A overestimated thigh muscle volume (MRI mean, 2.3 l) substantially (bias 0.36 l), whereas model B underestimated it by only 2% (bias 0.045 l). Lower leg muscle (MRI mean, 0.6 l) was better predicted using model A (bias 0.04 l, 7% overestimate) than model B (bias 0.1 l, 17% underestimate). The 95% limits of agreement were high for these models (thigh,+/- 20%; lower leg,+/- 47%). Model C predictions were more discrepant than those of model B. There was generally less agreement between MRI and all DXA models for AT. Measurement variability was generally less for DXA measurements of FFST (coefficient of variation 0.7 - 1.8%) and fat (0.8 - 3.3%) than model B estimates of muscle (0.5-2.6%) and AT (3.3 - 6.8%), respectively. Despite strong relationships between them, muscle mass was overestimated by creatinine excretion with highly variable predictability. CONCLUSION: This study has shown the value of DXA models for assessment of muscle and AT in leg sections, but suggests the need to re-evaluate some of the assumptions upon which they are based.

Body composition assessment of undernourished older subjects by dual-energy x-ray absorptiometry and bioelectric impedance analysis

The prevention and treatment of diseases related to changes in body composition require accurate methods for the measurement of body composition. However, few studies have dealt specifically with the assessment of body composition of undernourished older subjects by different methodologies. To assess the body composition of undernourished older subjects by two different methods, dual energy x-ray absorptiometry (DXA) and bioelectric impedance (BIA), and to compare results with those of an eutrophic group. The study model was cross-sectional; the study was performed at the University Hospital of the School of Medicine of Ribeiro Preto, University of So Paulo, Brazil. Forty-one male volunteers aged 62 to 91 years. The groups were selected on the basis of anamnesis, physical examination and nutritional assessment according to the Mini Nutritional Assessment (MNA) score. Body composition was assessed by DXA and BIA. Body weight, arm and calf circumference, body mass index (BMI), fat free mass (FFM) and fat mass (FM) were significantly lower in the undernourished group as compared to the eutrophic group. There were no significant differences between FFM and FM mean values determined by DXA and BIA in both groups, but the agreement between methods in the undernourished group was less strong. Our results suggest caution when BIA is to be applied in studies including undernourished older subjects. This study does not support BIA as an accurate method for the individual assessment of body composition.

Ligand K-edge X-ray absorption spectroscopy and DFT calculations on [Fe3S4]0,+ clusters: delocalization, redox, and effect of the protein environment

Ligand K-edge XAS of an [Fe3S4]0 model complex is reported. The pre-edge can be resolved into contributions from the í2Ssulfide, í3Ssulfide, and Sthiolate ligands. The average ligand-metal bond covalencies obtained from these pre-edges are further distributed between Fe3+ and Fe2.5+ components using DFT calculations. The bridging ligand covalency in the [Fe2S2]+ subsite of the [Fe3S4]0 cluster is found to be significantly lower than its value in a reduced [Fe2S2] cluster (38% vs 61%, respectively). This lowered bridging ligand covalency reduces the superexchange coupling parameter J relative to its value in a reduced [Fe2S2]+ site (-146 cm-1 vs -360 cm-1, respectively). This decrease in J, along with estimates of the double exchange parameter B and vibronic coupling parameter ì2/k-, leads to an S ) 2 delocalized ground state in the [Fe3S4]0 cluster. The S K-edge XAS of the protein ferredoxin II (Fd II) from the D. gigas active site shows a decrease in covalency compared to the model complex, in the same oxidation state, which correlates with the number of H-bonding interactions to specific sulfur ligands present in the active site. The changes in ligand-metal bond covalencies upon redox compared with DFT calculations indicate that the redox reaction involves a two-electron change (one-electron ionization plus a spin change of a second electron) with significant electronic relaxation. The presence of the redox inactive Fe3+ center is found to decrease the barrier of the redox process in the [Fe3S4] cluster due to its strong antiferromagnetic coupling with the redox active Fe2S2 subsite.

Espectroscopía de emisión de rayos x. Aplicación a la caracterización de materiales. X-ray emission spectroscopy. Application to materials characterization

La idea principal del proyecto abarca el estudio de parámetros y fenómenos físicos. Los avances logrados se aplicarán al desarrollo de software y metodologías para cuantificación de materiales mediante microanálisis con sonda de electrones y microscopía electrónica de barrido. El microanálisis no es una técnica absoluta, sino que requiere de estándares de referencia, para obviar el uso de ciertos parámetros geométricos y atómicos difíciles de conocer con una precisión adecuada. Para contar con un método sin estándares debe abordarse la determinación de parámetros atómicos e instrumentales, que es uno de los aspectos que se desea encarar en este proyecto. Por otro lado, también se pretende incluir los parámetros estudiados en un software de cuantificación desarrollado por integrantes del proyecto. Otro de los propósitos del plan de trabajo es estudiar la potencialidad de la resolución espacial de una microsonda de electrones con el fin de desarrollar una metodología para caracterizar interfases, bordes de granos e inclusiones, con resolución submicrométrica, ya que los métodos tradicionales de cuantificación se restringen al caso de muestras planas y homogéneas dentro del volumen de interacción, pero la caracterización de inhomogeneidades a nivel micrométrico no ha sido desarrollada todavía, salvo algunas excepciones. The main idea of this project involves the study of physical parameters and phenomena. The concretion of the different goals will permit the elaboration of softeare and methodologies for materials characterization by means of electron probe microanalysis and scanning microscopy. Electron probe microanalysis is not an absolute technique, but requires reference standards in order not to involve certain geometrical and atomic parameters for which high uncertainties cannot be avoided. In order to have standardless method, the determination of atomic and instrumental parameters must be accomplished, as will be faced through this project. Complementary, the parameters studied will be included in a quantification software developed in our research group of FaMAF. Another objective of this activity plan is to study the spatial resolution potentiality of a focalized electron beam, with the aim of characterizing interphases, grain boundaries and inclusions with submicron sensitivity, since the traditional quantification procedures are restricted to flat homogeneous samples, whereas the characterization of inhomogeneities has not been developed yet.

Creation of an Age-Adjusted, Dual-Energy X-ray Absorptiometry-Derived Trabecular Bone Score Curve for the Lumbar Spine in Non-Hispanic US White Women.

The trabecular bone score (TBS, Med-Imaps, Pessac, France) is an index of bone microarchitecture texture extracted from anteroposterior dual-energy X-ray absorptiometry images of the spine. Previous studies have documented the ability of TBS of the spine to differentiate between women with and without fractures among age- and areal bone mineral density (aBMD)-matched controls, as well as to predict future fractures. In this cross-sectional analysis of data collected from 3 geographically dispersed facilities in the United States, we investigated age-related changes in the microarchitecture of lumbar vertebrae as assessed by TBS in a cohort of non-Hispanic US white American women. All subjects were 30 yr of age and older and had an L1-L4aBMDZ-score within ±2 SD of the population mean. Individuals were excluded if they had fractures, were on any osteoporosis treatment, or had any illness that would be expected to impact bone metabolism. All data were extracted from Prodigy dual-energy X-ray absorptiometry devices (GE-Lunar, Madison, WI). Cross-calibrations between the 3 participating centers were performed for TBS and aBMD. aBMD and TBS were evaluated for spine L1-L4 but also for all other possible vertebral combinations. To validate the cohort, a comparison between the aBMD normative data of our cohort and US non-Hispanic white Lunar data provided by the manufacturer was performed. A database of 619 non-Hispanic US white women, ages 30-90 yr, was created. aBMD normative data obtained from this cohort were not statistically different from the non-Hispanic US white Lunar normative data provided by the manufacturer (p = 0.30). This outcome thereby indirectly validates our cohort. TBS values at L1-L4 were weakly inversely correlated with body mass index (r = -0.17) and weight (r = -0.16) and not correlated with height. TBS values for all lumbar vertebral combinations decreased significantly with age. There was a linear decrease of 16.0% (-2.47 T-score) in TBS at L1-L4 between 45 and 90 yr of age (vs. -2.34 for aBMD). Microarchitectural loss rate increased after age 65 by 50% (-0.004 to -0.006). Similar results were obtained for other combinations of lumbar vertebra. TBS, an index of bone microarchitectural texture, decreases with advancing age in non-Hispanic US white women. Little change in TBS is observed between ages 30 and 45. Thereafter, a progressive decrease is observed with advancing age. The changes we observed in these American women are similar to that previously reported for a French population of white women (r(2) > 0.99). This reference database will facilitate the use of TBS to assess bone microarchitectural deterioration in clinical practice.

Precision of a new tool to measure visceral adipose tissue (VAT) using dual-energy X-Ray absorptiometry (DXA).

OBJECTIVE: A new tool to quantify visceral adipose tissue (VAT) over the android region of a total body dual-energy x-ray absorptiometry (DXA) scan has recently been reported. The measurement, CoreScan, is currently available on Lunar iDXA densitometers. The purpose of the study was to determine the precision of the CoreScan VAT measurement, which is critical for understanding the utility of this measure in longitudinal trials. DESIGN AND METHODS: VAT precision was characterized in both an anthropomorphic imaging phantom (measured on 10 Lunar iDXA systems) and a clinical population consisting of obese women (n = 32). RESULTS: The intrascanner precision for the VAT phantom across 9 quantities of VAT mass (0-1,800 g) ranged from 28.4 to 38.0 g. The interscanner precision ranged from 24.7 to 38.4 g. There was no statistical dependence on the quantity of VAT for either the inter- or intrascanner precision result (p = 0.670). Combining inter- and intrascanner precision yielded a total phantom precision estimate of 47.6 g for VAT mass, which corresponds to a 4.8% coefficient of variance (CV) for a 1 kg VAT mass. Our clinical population, who completed replicate total body scans with repositioning between scans, showed a precision of 56.8 g on an average VAT mass of 1110.4 g. This corresponds to a 5.1% CV. Hence, the in vivo precision result was similar to the phantom precision result. CONCLUSIONS: The study suggests that CoreScan has a relatively low precision error in both phantoms and obese women and therefore may be a useful addition to clinical trials where interventions are targeted towards changes in visceral adiposity.