I08-Scanning X-ray Microscopy beamline (SXM)
|
Abstract: Fluoroacetate (FA), a plant toxin and intermediate product of anticancer agents, integrates itself into the Krebs cycle by substituting for acetate to form fluorocitrate. The function of this key metabolic cycle in glucose metabolism is disabled when fluorocitrate binds to aconitase. FA purportedly disrupts the Krebs cycle selectively in non-neuronal cells, i.e. glia/astrocytes, making it the substance of choice by which to assess the importance of glia for brain function in the living animal. However, since acetate, considered a marker of glial oxidative metabolism, can also be transported into neurons begs the question whether FA uptake, metabolism, and compartmentation is glial-selective in vivo, and whether this can be experimentally imaged; as important, is whether the first phase of brain glucose metabolism, i.e. glycolysis is affected. Dynamic cerebral 18FDG (glucose) PET in the living rat, and low energy x-ray fluorescence chemical imaging of such brains, albeit freeze substitution-fixed and epon infiltrated, were implemented to address these questions, and enabled testing our working hypothesis that sexual dimorphism of brain structure and function extends to metabolism as well.
|
Aug 2018
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Diamond Proposal Number(s):
[11016]
Open Access
Abstract: Glaciers and ice sheets are a significant source of nanoparticulate Fe, which is potentially important in sustaining the high productivity observed in the near-coastal regions proximal to terrestrial ice cover. However, the bioavailability of particulate iron is poorly understood, despite its importance in the ocean Fe inventory. We combined high-resolution imaging and spectroscopy to investigate the abundance, morphology and valence state of particulate iron in glacial sediments. Our results document the widespread occurrence of amorphous and Fe(II)-rich and Fe(II)-bearing nanoparticles in Arctic glacial meltwaters and iceberg debris, compared to Fe(III)-rich dominated particulates in an aeolian dust sample. Fe(II) is thought to be highly biolabile in marine environments. Our work shows that glacially derived Fe is more labile than previously assumed, and consequently that glaciers and ice sheets are therefore able to export potentially bioavailable Fe(II)-containing nanoparticulate material to downstream ecosystems, including those in a marine setting. Our findings provide further evidence that Greenland Ice Sheet meltwaters may provide biolabile particulate Fe that may fuel the large summer phytoplankton bloom in the Labrador Sea, and that Fe(II)-rich particulates from a region of very high productivity downstream of a polar ice sheet may be glacial in origin.
|
Jul 2018
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Diamond Proposal Number(s):
[15854, 19779]
Open Access
Abstract: Altered metabolism of biometals in the brain is a key feature of Alzheimer’s disease, and biometal interactions
with amyloid-β are linked to amyloid plaque formation. Iron-rich aggregates, including evidence
for the mixed-valence iron oxide magnetite, are associated with amyloid plaques. To test the hypothesis
that increased chemical reduction of iron, as observed in vitro in the presence of aggregating amyloid-β,
may occur at sites of amyloid plaque formation in the human brain, the nanoscale distribution and
physicochemical states of biometals, particularly iron, were characterised in isolated amyloid plaque cores
from human Alzheimer’s disease cases using synchrotron X-ray spectromicroscopy. In situ X-ray magnetic
circular dichroism revealed the presence of magnetite: a finding supported by ptychographic observation
of an iron oxide crystal with the morphology of biogenic magnetite. The exceptional sensitivity and
specificity of X-ray spectromicroscopy, combining chemical and magnetic probes, allowed enhanced
differentiation of the iron oxides phases present. This facilitated the discovery and speciation of ferrousrich
phases and lower oxidation state phases resembling zero-valent iron as well as magnetite.
Sequestered calcium was discovered in two distinct mineral forms suggesting a dynamic process of
amyloid plaque calcification in vivo. The range of iron oxidation states present and the direct observation
of biogenic magnetite provide unparalleled support for the hypothesis that chemical reduction of iron
arises in conjunction with the formation of amyloid plaques. These new findings raise challenging questions
about the relative impacts of amyloid-β aggregation, plaque formation, and disrupted metal homeostasis
on the oxidative burden observed in Alzheimer’s disease.
|
Apr 2018
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Diamond Proposal Number(s):
[14799, 17780]
Open Access
Abstract: We are investigating the effects of thermal meta-morphism on crystalline and amorphous silicates in the matrices of CO carbonaceous chondrites, which range in petrologic type from 3.0 to 3.8. Our aim is to better understand the initial formation conditions of the sili-cates, and to quantify how the degree of asteroidal heating has influenced their abundance, structure, chemistry and transformation behaviour. Here we pre-sent results from the CO chondrites DOM 08006 (CO 3.0), Kainsaz (CO 3.2) and Moss (CO 3.6).
|
Mar 2018
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Diamond Proposal Number(s):
[15994]
Abstract: Understanding the distribution of nanoparticles in skin layers is fundamentally important and essential for developing nanoparticle-based dermal drug delivery systems. In the present study, we provide insights into the distribution of gold nanorods (GNRs) functionalized with hydrophobic or hydrophilic ligands in human skin layers using synchrotron X-ray fluorescence (SR-XRF) spectroscopy, confocal microscopy, and transmission electron microscopy. The results confirmed the important role that the surface chemistry of GNRs plays in their penetration into the skin; the GNRs coated with polyethylene glycol were distributed into the skin layers to a greater extent than the GNRs coated with hydrophobic polystyrene thiol. In addition, SR-XRF analysis revealed that the spatial distribution of endogenous elements (phosphorus and sulfur) in skin layers demonstrated a significant “anti-correlation” relationship with that of GNRs. These results suggest possible association (via adsorption) between the GNRs and these two elements localized in skin, which can be valuable for understanding the penetration mechanism of gold nanoparticles into the skin.
|
Feb 2018
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Qing
Wu
,
Karolina
Soppa
,
Nadim
Scherrer
,
Benjamin
Watts
,
Tadahiro
Yokosawa
,
Laetitia
Bernard
,
Tohru
Araki
,
Max
Döbeli
,
Markus
Meyer
,
Erdmann
Spiecker
,
Rainer H.
Fink
Diamond Proposal Number(s):
[15595]
Open Access
Abstract: Zwischgold is a two-sided metal foil made by adhering a gold leaf over a silver leaf to present a gold surface while using less gold than gold foils. Corroded Zwischgold surfaces appear dark, accompanied by gloss loss and possible mechanical stability issues. Zwischgold applied artefacts are commonly found in museums and churches across Europe and they currently face an uncertain future as conservators have little knowledge to base conservation treatments on. We present a comprehensive material analysis of Zwischgold models through advanced characterization techniques including focused ion beam coupled with scanning electron microscopy (FIB-SEM), transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM), time-of-flight secondary ion mass spectrometry (TOF-SIMS)and Rutherford backscattering spectrometry (RBS). Complementary information on the foil thickness,sharpness of the gold-silver interface, gold purity, and the formation as well as distribution of corrosion products on Zwischgold models have been obtained, representing a starting point for understanding themorphology and the long-term chemistry of Zwischgold artefacts.
|
Jan 2018
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Diamond Proposal Number(s):
[11426]
Open Access
Abstract: Many studies have described petrographic evidence for in situ aqueous alteration
on the asteroid parent body(ies) of CM chondrites [1]. However, the origin of finegrained
rims (FGRs) of phyllosilicates that surround pristine anhydrous fragments in
CM chondrites remains controversial. The textures of FGRs suggest that they formed
through accretion onto their host objects, but it’s not clear whether hydration of the
dust occurred in a nebula [2] or asteroid [3] environment. The settings of aqueous
alteration in the early solar system may be inferred from crystal chemical variations
within the sub-micron mineralogy of FGRs and matrix within the CM chondrites.
Using synchrotron μXANES we observed systematic variations in Fe3+/ΣFe
across FGRs but not within the matrix [4]. To identify the source of this variation we
used STXM and nanoscale XRF to compare the crystal-chemical relationships of the
matrix mineralogy with that of the FGRs. Changes in Fe L- and O K-edge spectra
from matrix areas can be attributed to oxide and phyllosilicate minerals. For FGRs,
small changes in the relative intensities of the Fe L3 edge main peaks suggest
variations in the Fe3+/ΣFe ratio. More grain-scale variability is observed in the FGR
than in the matrix, and Fe-sulphides are detected in the FGR but not in the matrix.
Our data show that the composition of the FGR is mineralogically distinct from
the matrix, showing it was surrounding the chondrules in their nebular sojourn prior to
accretion and hence has sampled a different reservoir of dust to the matrix. A
possible explanation for the data is the incorporation of ice and/or carbonaceous
grains in the FGR which would cause local variability in redox states when these
phases reacted on the asteroidal parent body.
|
Dec 2017
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Abstract: The origin and formation of our Solar System is an open research question, which the scientific community is trying to address. In this work was specifically investigated the fine grained matrix which is a mixture of fine-grained materials composed largely of amorphous silicate and sub-micrometre crystals forsterite and enstatite. This is thought to be the remnants of the dust and gas of the protoplanetary disk that allows us to better understand chemical and physical properties of this precursor material. Four pristine primitive meteorites were selected: Acfer 094 (C2-ung.), ALHA77307 (CO3), MIL 07687 (C3-ung.) and QUE 99177 (CR2). The ability of a new generation of SEM-EDX detector was tested, in order to acquire high-resolution element maps of fine grained matrix. This allowed the calculation of abundances, and size distribution of discrete grains of different phases (silicate vs. opaque). Data acquired suggest that the four meteorites can be split into two groups, ALHA77307-MIL 07687 and QUE 99177 and Acfer 094, based on differences in relative abundances and sizes of discrete grains in their matrix. Micro X-ray diffraction was also used for mineralogical phase identification of the matrix constituents allowing the estimation of their modal mineralogy.
MIL 0768 and Acfer 094 were also investigated using Scanning Transmission X-ray Microscopy (STXM) which revealed predominantly oxidising conditions; some reducing conditions are also displayed by some grains, reflecting the mixed redox conditions of the solar nebula.
Measurements of O-isotopic composition of matrix regions were performed, and revealed similarities to values previously reported for IDPs (Starkey et al. 2013,2014 Nakashima et al., 2012, Aleon et al., 2009), rather than those of bulk meteorites (Clayton & Mayeda, 1999). I infer that the observed differences between these matrix components within the meteorite reflect the heterogeneity of the protoplanetary disk. Although these meteorites are pristine, parent body processes have also affected the small matrix grains.
|
Nov 2017
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Open Access
Abstract: Gold nanorods (GNRs) have been fabricated by a novel polymer-immobilised seed mediated method using ultraviolet (UV) photoreduced gold-polymethylmethacrylate
(Au–PMMA) nanocomposites as a seed platform and characterised at sub-micron scale regime with
synchrotron-based techniques; near-edge X-ray absorption fine structure (NEXAFS) spectroscopy
and X-ray fluorescence (XRF) mapping. In this report, it is shown that investigating polymer
nanocomposites using combination of XRF mapping and NEXAFS spectromicroscopy can help
to see the growth phenomenon from different perspective than conventional characterisation
techniques. XRF maps are used to explore distribution of the constituent elements and showing
how polymer matrix making stripe patterns along with regions where GNRs are formed. NEXAFS
carbon (C) K-edge spectra have been taken at three different stages of synthesis: (1) on Au–PMMA
nanocomposites before UV irradiation, (2) after gold nanoparticles formation, and (3) after GNRs formation. It reveals how polymer matrix has been degraded during GNRs formation and avoiding chemically or physically damage to polymer matrix is crucial to control the formation of GNRs.
|
Oct 2017
|
|
I08-Scanning X-ray Microscopy beamline (SXM)
|
Diamond Proposal Number(s):
[11282]
Abstract: Rivers are significant contributors of Fe to the ocean. However, the characteristics of chemically reactive Fe remain poorly constrained, especially in large Arctic rivers, which drain landscapes highly susceptible to climate change and carbon cycle alteration. The aim of this study was a detailed characterisation (size, mineralogy, and speciation) of riverine Fe-bearing particles (> 0.22 µm) and colloids (1 kDa – 0.22 µm) and their association with organic carbon (OC), in the Lena River and tributaries, which drain a catchment almost entirely underlain by permafrost. Samples from the main channel and tributaries representing watersheds that span a wide range in topography and lithology were taken after the spring flood in June 2013 and summer baseflow in July 2012. Fe-bearing particles were identified, using Transmission Electron Microscopy, as large (200 nm – 1 µm) aggregates of smaller (20 nm - 30 nm) spherical colloids of chemically-reactive ferrihydrite. In contrast, there were also large (500 nm – 1 µm) aggregates of clay (illite) particles and smaller (100 - 200 nm) iron oxide particles (dominantly hematite) that contain poorly reactive Fe. TEM imaging and Scanning Transmission X-ray microscopy (STXM) indicated that the ferrihydrite is present as discrete particles within networks of amorphous particulate organic carbon (POC) and attached to the surface of primary produced organic matter and clay particles. Together, these larger particles act as the main carriers of nanoscale ferrihydrite in the Lena River basin. The chemically reactive ferrihydrite accounts for on average 70 ± 15 % of the total suspended Fe in the Lena River and tributaries. These observations place important constraints on Fe and OC cycling in the Lena River catchment area and Fe-bearing particle transport to the Arctic Ocean.
|
Jul 2017
|
|