Transmission X-ray Microscopy Measurements Research Articles

Elemental changes in heart and coronaries after breast cancer radiotherapy assessed by synchrotron radiation soft X-ray spectromicroscopy

Radiotherapy (RT) plays a pivotal role in the treatment of breast cancer (BC) and various thoracic malignancies. Radiation induced heart disease (RIHD) is one such long term toxicity which can offset the improvement in cancer specific mortality. Long term normal tissue toxicity is becoming a bigger concern, as early diagnosis and the improvement in the treatment of these cancers has led to patients surviving longer. Our research group on Physics applied to biomedical sciences has been investigating the side effects of BC treatment (RT and chemotherapy) for more than ten years. The cardiac regeneration has been studied to better understand the damage that occurs following radiation procedures in the heart tissue after many thoracic cancer treatments. One possible complication is coronary artery disease induced by irradiation after radiotherapy in thoracic area. Studies on the structures of cardiac tissue and the distribution of low atomic weight element can help to understand mechanisms associated with damage to healthy tissue, as these are of fundamental importance to metabolism in biological systems. The present study aimed to elucidate how radiotherapy in the thoracic area causes damage in the coronary artery, and to verify the potential use of losartan in reducing, or even preventing, the side effects of irradiation in this artery. To assess elemental and morphological differences in aortic and coronary samples, the Low Energy X-Ray Fluorescence (LEXRF) technique using Synchrotron Radiation was employed. SR- LEXRF and scanning transmission X-ray microscopy measurements were carried out at the beamline TwinMic at Elettra Sincrotrone Triste, Italy.

Formation of Néel-type skyrmions in an antidot lattice with perpendicular magnetic anisotropy

Magnetic skyrmions are particle-like chiral spin textures found in a magnetic film with out-of-planeanisotropy and are considered to be potential candidates as information carriers in next generationdata storage devices. Despite intense research into the nature of skyrmions and their dynamic prop-erties, there are several key challenges that still need to be addressed. In particular, the outstandingissues are the reproducible generation, stabilization and confinement of skyrmions at room tempera-ture. Here, we present a method for the capture of nanometer sized magnetic skyrmions in an arrayof magnetic topological defects in the form of an antidot lattice. With micromagnetic simulations,we elucidate the skyrmion formation in the antidot lattice and show that the capture is dependenton the antidot lattice parameters. This behavior is confirmed with scanning transmission x-ray mi-croscopy measurements. This demonstration that a magnetic antidot lattice can be implemented asa host to capture skyrmions provides a new platform for experimental investigations of skyrmionsand skyrmion based devices.

Polarization dependent X-ray absorption near-edge spectra of boron nitride nanotubes

We report polarization dependent, scanning transmission X-ray microscopy measurements of individual boron nitride nanotubes (BNNTs) and analyze them by means of first-principles calculations. X-ray absorption near-edge spectra of hexagonal boron-nitride (hBN) are calculated as a function of light polarization and layer stacking and best agreement with recent experimental data is obtained for the commonly assumed AA' stacking. Our experimental BNNT spectra show a pronounced polarization dependence which is qualitatively well reproduced in the calculations. We show that the BNNT has a mixed stacking sequence which may explain some of the differences seen between the hBN and BNNT line shapes.

Roadblocks in Cation Diffusion Pathways: Implications of Phase Boundaries for Li-Ion Diffusivity in an Intercalation Cathode Material.

Increasing intercalation of Li-ions brings about distortive structural transformations in several canonical intercalation hosts. Such phase transformations require the energy dissipative creation and motion of dislocations at the interface between the parent lattice and the nucleated Li-rich phase. Phase inhomogeneities within particles and across electrodes give rise to pronounced stress gradients, which can result in capacity fading. How such transformations alter Li-ion diffusivities remains much less explored. In this article, we use layered V2O5 as an intercalation host and examine the structural origins of the evolution of Li-ion diffusivities with phase progression upon electrochemical lithiation. Galvanostatic intermittent titration measurements show a greater than 4 orders of magnitude alteration of Li-ion diffusivity in V2O5 as a function of the extent of lithiation. Pronounced dips in Li-ion diffusivities are correlated with the presence of phase mixtures as determined by Raman spectroscopy and X-ray diffraction, whereas monophasic regimes correspond to the highest Li-ion diffusivity values measured within this range. First-principles density functional theory calculations confirm that the variations in Li-ion diffusivity do not stem from intrinsic differences in diffusion pathways across the different lithiated V2O5 phases, which despite differences in the local coordination environments of Li-ions show comparable migration barriers. Scanning transmission X-ray microscopy measurements indicate the stabilization of distinct domains reflecting the phase coexistence of multiple lithiated phases within individual actively intercalating particles. The results thus provide fundamental insight into the considerable ion transport penalties incurred as a result of phase boundaries formed within actively intercalating particles. The combination of electrochemical studies with ensemble structural characterization and single-particle X-ray imaging of phase boundaries demonstrates the profound impact of interfacial phenomena on macroscopic electrode properties.

Point focusing with flat and wedged crossed multilayer Laue lenses.

Point focusing measurements using pairs of directly bonded crossed multilayer Laue lenses (MLLs) are reported. Several flat and wedged MLLs have been fabricated out of a single deposition and assembled to realise point focusing devices. The wedged lenses have been manufactured by adding a stress layer onto flat lenses. Subsequent bending of the structure changes the relative orientation of the layer interfaces towards the stress-wedged geometry. The characterization at ESRF beamline ID13 at a photon energy of 10.5 keV demonstrated a nearly diffraction-limited focusing to a clean spot of 43 nm × 44 nm without significant side lobes with two wedged crossed MLLs using an illuminated aperture of approximately 17 µm × 17 µm to eliminate aberrations originating from layer placement errors in the full 52.7 µm × 52.7 µm aperture. These MLLs have an average individual diffraction efficiency of 44.5%. Scanning transmission X-ray microscopy measurements with convenient working distances were performed to demonstrate that the lenses are suitable for user experiments. Also discussed are the diffraction and focusing properties of crossed flat lenses made from the same deposition, which have been used as a reference. Here a focal spot size of 28 nm × 33 nm was achieved and significant side lobes were noticed at an illuminated aperture of approximately 23 µm × 23 µm.

Phase evolution in single-crystalline LiFePO₄ followed by in situ scanning X-ray microscopy of a micrometre-sized battery.

LiFePO₄ is one of the most frequently studied positive electrode materials for lithium-ion batteries during the last years. Nevertheless, there is still an extensive debate on the mechanism of phase transformation. On the one hand this is due to the small energetic differences involved and hence the great sensitivity with respect to parameters such as size and morphology. On the other hand this is due to the lack of in situ observations with appreciable space and time resolution. Here we present scanning transmission X-ray microscopy measurements following in situ the phase boundary propagation within a LiFePO₄ single crystal along the (010) orientation during electrochemical lithiation/delithiation. We follow, on a battery-relevant timescale, the evolution of a two-phase-front on a micrometre scale with a lateral resolution of 30 nm and with minutes of time resolution. The growth pattern is found to be dominated by elastic effects rather than being transport-controlled.

Pressure-induced densification in GeO2 glass: A transmission x-ray microscopy study

Nanoscale transmission x-ray microscopy measurements have been performed to determine the effect of pressure (P) on the volume (V) change in GeO2 glass up to 38.5 GPa. The P-V data show a continuous increase upon compression, indicating that the density-driven structural transformation is a gradual process. Over the pressure range studied, a transition is observed at approximately 10–13 GPa, where the material displays distinct compression behaviors. The pressure-induced densification that involves the coordination number change has been discussed. Using this newly developed high-pressure imaging technique with tens of nanometer resolution, we have provided a direct and unequivocal way for measuring density of amorphous materials to much higher pressures with accuracy rivaling x-ray diffraction of crystalline solids.

An environmental sample chamber for reliable scanning transmission x-ray microscopy measurements under water vapor

We have designed, fabricated, and tested a compact gas-phase reactor for performing in situ soft x-ray scanning transmission x-ray microscopy (STXM) measurements. The reactor mounts directly to the existing sample holder used in the majority of STXM instruments around the world and installs with minimal instrument reconfiguration. The reactor accommodates many gas atmospheres, but was designed specifically to address the needs of measurements under water vapor. An on-board sensor measures the relative humidity and temperature inside the reactor, minimizing uncertainties associated with measuring these quantities outside the instrument. The reactor reduces x-ray absorption from the process gas by over 85% compared to analogous experiments with the entire STXM instrument filled with process gas. Reduced absorption by the process gas allows data collection at full instrumental resolution, minimizes radiation dose to the sample, and results in much more stable imaging conditions. The reactor is in use at the STXM instruments at beamlines 11.0.2 and 5.3.2.2 at the Advanced Light Source.

Three-dimensional morphological measurements of LiCoO2 and LiCoO2/Li(Ni1/3Mn1/3Co1/3)O2 lithium-ion battery cathodes

The three-dimensional (3D) morphologies of two types of lithium-ion battery cathodes, LiCoO2 (LCO) and LiCoO2/Li(Ni1/3Mn1/3Co1/3)O2 (LCO/NMC) composites, have been measured using focused ion beam – scanning electron microscopy (FIB-SEM) and transmission X-ray microscopy (TXM). TXM measurements were taken at X-ray energies that can provide clear contrast between LCO and NMC particles in the composite cathodes. Multiple three-dimensional image volumes were collected and statistical analyses were done to assess the accuracy and spatial variation of structural parameters including oxide volume fractions, surface areas, and particle size distributions. Comparisons of un-cycled and cycled batteries showed small changes in structure, but spatial and cell-to-cell microstructural variations, found especially in the LCO/NMC cathodes, were large enough to limit the ability to distinguish actual cycling-induced structure changes. The observation of cathode metal cations on the battery anode after cycling may explain, at least in part, the observed ∼30% capacity loss.

Sub‐Micrometer Charge Modulation Microscopy of a High Mobility Polymeric n‐Channel Field‐Effect Transistor

Electro-optical mapping of the charge density with sub-micrometer resolution can be obtained in a high mobility, top-gate n-channel polymer field-effect transistor by charge modulation microscopy. Local features on the 1 μm scale are unveiled and, using scanning transmission X-ray microscopy measurements, are attributed to structural variations within the polymeric film.

Insulating behavior of magnetic spots in proton-bombarded graphite

Kelvin probe force microscopy measurements on micrometer small magnetic spots produced by proton bombardment on bulk graphite reveal a charge transfer from the center of the spot to an external ring with potential variation on the order of 50 mV. The total charge in the spot is neutral. The results can be well understood in terms of practically unscreened potentials, an insulating property, although the nonbombarded, surrounding graphite region exhibits good conductance. Scanning transmission x-ray microscopy measurements on magnetic spots prepared on graphitic films reveal similar charge distribution. The insulating behavior is fundamental to understand the magnetism in graphite.

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca5(PO4)3.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO4·H2O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce3+ ions oxidizing to CeO2. Reaction product analysis shows the formation of CO2, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M4,5 and C-K absorption edges on reacted CePO4·H2O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO4·H2O and O2 but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π∗ resonances due to carbon in carboxyl (ca. 288.5eV) and carbonyl (ca. 289.3eV) groups, and the development of broad structure in the σ∗ region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O2 (aq) causes both the oxidation of structural Ce3+ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO2, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π∗ resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O2, CeO2 can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO2 particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.