Evan R. Maxey

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. Here we study the hydriding phase transformation in individual palladium nanocubes in situ using coherent X-ray diffractive imaging. The phase transformation dynamics, which involve the nucleation and propagation of a hydrogen-rich region, are dependent on absolute time (aging) and involve intermittent dynamics (avalanching). A hydrogen-rich surface layer dominates the crystal strain in the hydrogen-poor phase, while strain inversion occurs at the cube corners in the hydrogen-rich phase. A three-dimensional phase-field model is used to interpret the experimental results. Our experimental and theoretical approach provides a general framework for designing and optimizing phase transformations for single nanocrystals in reactive environments.

Direct observation of adsorbed H2-framework interactions in the Prussian Blue analogue MnII3[CoIII(CN)6]2 : The relative importance of accessible coordination sites and van der Waals interactions

Selective recovery of the guest-framework interactions for H(2) adsorbed in a nanoporous Prussian Blue analogue, through differential X-ray and neutron pair distribution function analysis at ca. 77 K, suggests that the H(2) molecule is disordered about a single position at the centre of the pore, ((1/4),(1/4),(1/4)), without binding at accessible Mn(II) sites.

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). Local strains were measured in single nanoparticles and modeled using reactive molecular dynamics (RMD) simulations and finite element analysis (FEA) simulations. RMD reveals the pathway for local strain generation in the gold lattice: chemisorption of hydroxyl ions. FEA reveals that the RMD results are transferable to the nanocrystal sizes studied in the experiment. Our study probes the strain-activity connection and opens a powerful avenue for theoretical and experimental studies of nanocrystal catalysis.

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

A combination of Bragg coherent diffractive imaging and reciprocal-space mapping results indicate that the global radiation damage behaviour of micro-crystals is different compared with macroscale crystals.

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. For the critical angle of Pt, a broad bandwidth of energies up to 20 keV applies. The classical K-B sequential mirror geometry was used, and mirrors were mounted on micro-translation stages. The beam intensity profiles were measured by differentiating the curves of intensity data measured using a wire-scanning method. A beam size of 1.3 µm (V) and 1.2 µm (H) was measured with monochromatic X-rays of 18 keV at 1-BM. After installation at 8-BM the measured focus met the design requirements. In this paper the fabrication and metrology of the K-B mirrors are reported, as well as the focusing performances of the full mirrors-plus-mount set-up at both beamlines.

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

ABSTRACT 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. The release rates of cis‐platinum from liposomes composed of SML are a function of the acyl chain length. SML‐liposomes with shorter acyl chain lengths C‐8 provided more rapid cisplatin release, lower in vitro IC50, and were easier to formulate compared to liposomes using traditional phospholipid compositions. Similar to other liposome cis‐platinum formulations, the half‐life of m‐PEG‐DSPE SML liposome cisplatin is substantially longer than the free drug. This resulted in a higher tumor cisplatin concentration at 48 h post‐dosing compared to the free drug and higher Pt‐DNA adducts in the tumor. Moreover, the maximum tolerated dose of the liposome formulations where up to four fold greater than the free drug. Using X‐ray fluorescence spectroscopy on tumor sections, we compared the location of platinum, to the location of a fluorescence lipid incorporated in the liposomes. The liposome platinum co‐localized with the fluorescent lipid and both were non‐uniformly distributed in the tumor. Non‐encapsulated Cis‐platinum, albeit at a low concentration, was more uniformly distributed thorough the tumor. Three liposome formulations, including the well‐studied hydrogenated HSPC composition, had better antitumor activity in the murine colon 26 carcinoma model as compared to the free drug at the same dose but the SML liposome platinum formulations did not perform better than the HSPC formulation.

Fungal–copper interactions in wood examined with large field of view synchrotron-based X-ray fluorescence microscopy

ABSTRACT The goal of this study was to demonstrate how synchrotron-based X-ray fluorescence microscopy (XFM) can be used to better understand the mechanisms of copper tolerance in wood decay fungi. Copper is a major component in commercial wood preservatives as it is toxic to many wood decay fungi. However, certain fungi are copper tolerant and can attack preservative-treated wood, resulting in structural damage to treated wood members. Here we used large-field XFM to visualize six different elements (K, Ca, Mn, Fe, Cu, and Zn) in the mycelia and wood inoculated with four different species of brown rot wood decay fungi. Wood blocks were partially dipped into a solution of copper sulfate, exposed to fungi in malt extract agar petri dish assays for nine weeks, and then imaged and compared to blocks that were partially dipped in water. The blocks were imaged immediately adjacent to an end-matched control that was placed in malt extract agar petri dish assays for 9 weeks, but not exposed to the fungi so that the differences in the elemental distributions could be directly compared. The colonized wood and mycelia were rich in K, Ca, Mn, and Fe; however, the elements and the spatial distribution in the mycelia and wood differed across fungal species. The most interesting results were the maps showing the copper distribution. While three of the four fungi grew on the copper-rich region of the wood, only one species, Fibroporia radiculosa, dramatically reduced the copper concentration in the region of fungal growth.

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. Quantification of NPs in tissues was done both by bulk inductively coupled plasma mass spectrometry (ICP-MS) analysis and by hard X-ray fluorescence microscopy. Both IV and IC NPs injection are feasible modalities for delivering NPs to VX2 liver tumors with comparable tumor accumulation. It is possible that this is an outcome of the fact that VX2 tumors are highly vascularized and hemorrhagic, and therefore enhanced permeability and retention (EPR) plays the most significant role in accumulation of nanoparticles in tumor tissue. It is, however, interesting to note that IV delivery led to increased sequestration of NPs by spleen and normal liver tissue, while IC delivery lead to more NP positive Kupffer cells. This difference is most likely a direct outcome of blood flow dynamics. Armed with this knowledge about nanoparticle delivery, we plan to test them as radiosensitizers in the future.

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. Using the new protocol, we performed an initial compositional classification of a set of 83 ceramic shards from the western slopes of the south central Andean region in the Arica y Parinacota region (Chile). Comparing the classifications obtained using the new versus the old (average concentrations only) protocols, we found that some samples were erroneously classified with the old protocol. From an archaeological perspective, a broad and heterogeneous regional sample set was used in this experimental study due to the fact that this was the first such analysis to be performed on ceramics from this region. This allowed a general overview to be obtained, however further work on more specific sample sets will be necessary to extract concrete archaeological conclusions.

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. Here, using X-ray Bragg coherent diffraction imaging, we describe the first direct 3D X-ray imaging of the strain field surrounding a line defect within a grain of free-standing nanocrystalline material following tensile loading. By integrating the observed 3D structure into an atomistic model, we show that the measured strain field corresponds to a screw dislocation.Identifying atomic defects during deformation is crucial to understand material response but remains challenging in three dimensions. Here, the authors couple X-ray Bragg coherent diffraction imaging and atomistic simulations to correlate a strain field to a screw dislocation in a single copper grain.