Proof of principle study: synchrotron X-ray fluorescence microscopy for identification of previously radioactive microparticles and elemental mapping of FFPE tissues.

Biobanks containing formalin-fixed, paraffin-embedded (FFPE) tissues from animals and human atomic-bomb survivors exposed to radioactive particulates remain a vital resource for understanding the molecular effects of radiation exposure. These samples are often decades old and prepared using harsh fixation processes which limit sample imaging options. Optical imaging of hematoxylin and eosin (H&E) stained tissues may be the only feasible processing option, however, H&E images provide no information about radioactive microparticles or radioactive history.

Microstructure and energy dispersive diffraction reconstruction of 3D patterns of crystallographic texture in a shark centrum.

Tomography using diffracted x-rays produces reconstructions mapping quantities such as crystal lattice parameter(s), crystallite size, and crystallographic texture, information quite different from that obtained with absorption or phase contrast. Diffraction tomography is used to map an entire blue shark centrum with its double cone structure (corpora calcerea) and intermedialia (four wedges). Energy dispersive diffraction (EDD) and polychromatic synchrotron x-radiation at 6-BM-B, the Advanced Photon Source, were used.

Use of X-Ray Fluorescence Microscopy for Studies on Research Models of Hepatocellular Carcinoma.

TheraSphere microspheres containing yttrium Y are among many radioembolization agents used clinically to reduce liver tumor burden, and their effects on cancer volume reduction are well-established. At the same time, concerns about off target tissue injury often limit their use. Deeper investigation into tissue distribution and long-term impact of these microspheres could inform us about additional ways to use them in practice.

Paramagnetic MnFe--Polystyrene Nanobeads as a Potential T-T Multimodal Magnetic Resonance Imaging Contrast Agent with Studies.

In developing a cluster-nanocarrier design, as a magnetic resonance imaging contrast agent, we have investigated the enhanced relaxivity of a manganese and iron-oxo cluster grafted within a porous polystyrene nanobead with increased relaxivity due to a higher surface area. The synthesis of the cluster-nanocarrier for the cluster MnFeO(OCCHCH═CH)(HO), cross-linked with polystyrene (the nanocarrier), under miniemulsion conditions is described. By including a branched hydrophobe, -octane, the resulting nanobeads are porous and ∼70 nm in diameter.

Electrochemically Induced Strain Evolution in Pt-Ni Alloy Nanoparticles Observed by Bragg Coherent Diffraction Imaging.

Strain is known to enhance the activity of the oxygen reduction reaction in catalytic platinum alloy nanoparticles, whose inactivity is the primary impediment to efficient fuel cells and metal-air batteries. Bragg coherent diffraction imaging (BCDI) was employed to reveal the strain evolution during the voltammetric cycling in Pt-Ni alloy nanoparticles composed of PtNi, PtNi, and PtNi. Analysis of the 3D strain images using a core-shell model shows that the strain as large as 5% is induced on Pt-rich shells due to Ni dissolution.

Multi-beam X-ray ptychography for high-throughput coherent diffraction imaging.

X-ray ptychography is a rapidly developing coherent diffraction imaging technique that provides nanoscale resolution on extended field-of-view. However, the requirement of coherence and the scanning mechanism limit the throughput of ptychographic imaging. In this paper, we propose X-ray ptychography using multiple illuminations instead of single illumination in conventional ptychography.

Gas-Induced Segregation in Pt-Rh Alloy Nanoparticles Observed by In Situ Bragg Coherent Diffraction Imaging.

Bimetallic catalysts can undergo segregation or redistribution of the metals driven by oxidizing and reducing environments. Bragg coherent diffraction imaging (BCDI) was used to relate displacement fields to compositional distributions in crystalline Pt-Rh alloy nanoparticles. Three-dimensional images of internal composition showed that the radial distribution of compositions reverses partially between the surface shell and the core when gas flow changes between O_{2} and H_{2}.

Elemental Zn and its Binding Protein Zinc-α2-Glycoprotein are Elevated in HPV-Positive Oropharyngeal Squamous Cell Carcinoma.

Human papillomavirus (HPV)-positive head and neck squamous cell carcinoma (HNSCC) is biologically distinct from HPV-negative HNSCC. Outside of HPV-status, few tumor-intrinsic variables have been identified that correlate to improved survival. As part of exploratory analysis into the trace elemental composition of oropharyngeal squamous cell carcinoma (OPSCC), we performed elemental quanitification by X-ray fluorescence microscopy (XFM) on a small cohort (n = 32) of patients with HPV-positive and -negative OPSCC and identified in HPV-positive cases increased zinc (Zn) concentrations in tumor tissue relative to normal tissue.

three-dimensional imaging of strain in gold nanocrystals during catalytic oxidation.

The chemical properties of materials are dependent on dynamic changes in their three-dimensional (3D) structure as well as on the reactive environment. We report an 3D imaging study of defect dynamics of a single gold nanocrystal. Our findings offer an insight into its dynamic nanostructure and unravel the formation of a nanotwin network under CO oxidation conditions.

Localization of the Locus Coeruleus in the Mouse Brain.

The locus coeruleus (LC) is a major hub of norepinephrine producing neurons that modulate a number of physiological functions. Structural or functional abnormalities of LC impact several brain regions including cortex, hippocampus, and cerebellum and may contribute to depression, bipolar disorder, anxiety, as well as Parkinson disease and Alzheimer disease. These disorders are often associated with metal misbalance, but the role of metals in LC is only partially understood.

Methods for operando coherent X-ray diffraction of battery materials at the Advanced Photon Source.

Bragg coherent X-ray diffraction imaging has become valuable for visualization of the structural, morphological and strain evolution of crystals in operando electrode materials. As the electrode material particles (either in a single-crystal form or an aggregation form of single crystals) are evenly dispersed and randomly oriented in the electrode laminate, the submicrometer-sized coherentX-ray beam can be used to probe the local properties of electrode material crystals using two approaches. Coherent multi-crystal diffraction provides collective structural information of phase transitions in tens of crystals simultaneously as well as the individual behavior from single crystals, which are oriented at the Bragg condition in the X-ray illumination volume.

Three-dimensional X-ray diffraction imaging of dislocations in polycrystalline metals under tensile loading.

The nucleation and propagation of dislocations is an ubiquitous process that accompanies the plastic deformation of materials. Consequently, following the first visualization of dislocations over 50 years ago with the advent of the first transmission electron microscopes, significant effort has been invested in tailoring material response through defect engineering and control. To accomplish this more effectively, the ability to identify and characterize defect structure and strain following external stimulus is vital.

Active site localization of methane oxidation on Pt nanocrystals.

High catalytic efficiency in metal nanocatalysts is attributed to large surface area to volume ratios and an abundance of under-coordinated atoms that can decrease kinetic barriers. Although overall shape or size changes of nanocatalysts have been observed as a result of catalytic processes, structural changes at low-coordination sites such as edges, remain poorly understood. Here, we report high-lattice distortion at edges of Pt nanocrystals during heterogeneous catalytic methane oxidation based on in situ 3D Bragg coherent X-ray diffraction imaging.

Encapsulation, controlled release, and antitumor efficacy of cisplatin delivered in liposomes composed of sterol-modified phospholipids.

We employed a recently introduced class of sterol-modified lipids (SML) to produce m-PEG-DSPE containing liposome compositions with a range of cis-platinum content release rates. SML have a cholesterol succinate attached to the phosphatidylglycerol head group and a fatty acid at the 2 position. These compositions were compared to the well-studied liposome phospholipid compositions: mPEG-DSPE/Hydrogenated Soy PC/cholesterol or mPEG-DSPE/POPC/cholesterol to determine the effect of the cis-platinum release extent on C26 tumor proliferation in the BALB/c colon carcinoma mouse model.

Stability Limits and Defect Dynamics in Ag Nanoparticles Probed by Bragg Coherent Diffractive Imaging.

Dissolution is critical to nanomaterial stability, especially for partially dealloyed nanoparticle catalysts. Unfortunately, highly active catalysts are often not stable in their reactive environments, preventing widespread application. Thus, focusing on the structure-stability relationship at the nanoscale is crucial and will likely play an important role in meeting grand challenges.

Three-dimensional imaging of dislocation dynamics during the hydriding phase transformation.

Crystallographic imperfections significantly alter material properties and their response to external stimuli, including solute-induced phase transformations. Despite recent progress in imaging defects using electron and X-ray techniques, in situ three-dimensional imaging of defect dynamics remains challenging. Here, we use Bragg coherent diffractive imaging to image defects during the hydriding phase transformation of palladium nanocrystals.

Microdistribution of lead in human teeth using microbeam synchrotron radiation X-ray fluorescence (μ-SRXRF).

Lead (Pb) exposure is known to be associated with adverse effects on human health, especially during the prenatal period and early childhood. The Pb content in teeth has been suggested as a useful biomarker for the evaluation of cumulative Pb exposure. This study was designed to employ the microbeam synchrotron radiation X-ray fluorescence technique to determine the microdistribution of Pb within the tooth to evaluate the reliability of the technique and the effectiveness of tooth Pb as a biomarker of Pb exposure.

Bragg coherent diffraction imaging and metrics for radiation damage in protein micro-crystallography.

The proliferation of extremely intense synchrotron sources has enabled ever higher-resolution structures to be obtained using data collected from smaller and often more imperfect biological crystals (Helliwell, 1984). Synchrotron beamlines now exist that are capable of measuring data from single crystals that are just a few micrometres in size. This provides renewed motivation to study and understand the radiation damage behaviour of small protein crystals.

Cementum structure in Beluga whale teeth.

Unlabelled: A large fraction of the volume of Beluga whale (Delphinapterus leucas) teeth consists of cementum, a mineralized tissue which grows throughout the life of the animal and to which the periodontal ligaments attach. Annular growth bands or growth layer groups (GLGs) form within Beluga cementum, and this study investigates GLG structure using X-ray fluorescence mapping and X-ray diffraction mapping with microbeams of synchrotron radiation. The Ca and Zn fluorescent intensities and carbonated hydroxyapatite (cAp) diffracted intensities rise and fall together and match the light-dark bands visible in transmitted light micrographs.

Micro X-ray Fluorescence Study of Late Pre-Hispanic Ceramics from the Western Slopes of the South Central Andes Region in the Arica y Parinacota Region, Chile: A New Methodological Approach.

Archeological ceramic paste material typically consists of a mix of a clay matrix and various millimeter and sub-millimeter sized mineral inclusions. Micro X-ray fluorescence (XRF) is a standard compositional classification tool and in this work we propose and demonstrate an improved fluorescence map processing protocol where the mineral inclusions are automatically separated from the clay matrix to allow independent statistical analysis of the two parts. Application of this protocol allowed us to enhance the discrimination between different ceramic shards compared with the standard procedure of working with only the spatially averaged elemental concentrations.

In Situ 3D Imaging of Catalysis Induced Strain in Gold Nanoparticles.

Multielectron transfer processes are crucially important in energy and biological science but require favorable catalysts to achieve fast kinetics. Nanostructuring catalysts can dramatically improve their properties, which can be difficult to understand due to strain- and size-dependent thermodynamics, the influence of defects, and substrate-dependent activities. Here, we report three-dimensional (3D) imaging of single gold nanoparticles during catalysis of ascorbic acid decomposition using Bragg coherent diffractive imaging (BCDI).

Distribution of Iron Oxide Core-Titanium Dioxide Shell Nanoparticles in VX2 Tumor Bearing Rabbits Introduced by Two Different Delivery Modalities.

This work compares intravenous (IV) versus fluoroscopy-guided transarterial intra-catheter (IC) delivery of iron oxide core-titanium dioxide shell nanoparticles (NPs) in vivo in VX2 model of liver cancer in rabbits. NPs coated with glucose and decorated with a peptide sequence from cortactin were administered to animals with developed VX2 liver cancer. Two hours after NPs delivery tumors, normal liver, kidney, lung and spleen tissues were harvested and used for a series on histological and elemental analysis tests.

Avalanching strain dynamics during the hydriding phase transformation in individual palladium nanoparticles.

Phase transitions in reactive environments are crucially important in energy and information storage, catalysis and sensors. Nanostructuring active particles can yield faster charging/discharging kinetics, increased lifespan and record catalytic activities. However, establishing the causal link between structure and function is challenging for nanoparticles, as ensemble measurements convolve intrinsic single-particle properties with sample diversity.

Kirkpatrick-Baez mirrors to focus hard X-rays in two dimensions as fabricated, tested and installed at the Advanced Photon Source.

The micro-focusing performance for hard X-rays of a fixed-geometry elliptical Kirkpatrick-Baez (K-B) mirrors assembly fabricated, tested and finally implemented at the micro-probe beamline 8-BM of the Advanced Photon Source is reported. Testing of the K-B mirror system was performed at the optics and detector test beamline 1-BM. K-B mirrors of length 80 mm and 60 mm were fabricated by profile coating with Pt metal to produce focal lengths of 250 mm and 155 mm for 3 mrad incident angle.

X-ray absorption spectroscopy of metalloproteins.

Metalloproteins are enormously important in biology. While a variety of techniques exist for studying metals in biology, X-ray absorption spectroscopy is particularly useful in that it can determine the local electronic and physical structure around the metal center, and is one of the few avenues for studying "spectroscopically silent" metal ions like Zn(II) and Cu(I) that have completely filled valence bands. While X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) are useful for studying metalloprotein structure, they suffer the limitation that the detected signal is an average of all the various metal centers in the sample, which limits its usefulness for studying metal centers in situ or in cell lysates.