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Abstract: Woodlice efficiently sequester copper (Cu) in ‘cuprosomes' within hepatopancreatic ‘S' cells. Binuclear ‘B’ cells in the hepatopancreas form iron (Fe) deposits; these cells apparently undergo an apocrine secretory diurnal cycle linked to nocturnal feeding. Synchrotron-based µ-focus X-ray spectroscopy undertaken on thin sections was used to characterize the ligands binding Cu and Fe in S and B cells of Oniscus asellus (Isopoda). Main findings were: (i) morphometry confirmed a diurnal B-cell apocrine cycle; (ii) X-ray fluorescence (XRF) mapping indicated that Cu was co-distributed with sulfur (mainly in S cells), and Fe was co-distributed with phosphate (mainly in B cells); (iii) XRF mapping revealed an intimate morphological relationship between the basal regions of adjacent S and B cells; (iv) molecular modelling and Fourier transform analyses indicated that Cu in the reduced Cu+ state is mainly coordinated to thiol-rich ligands (Cu–S bond length 2.3 Å) in both cell types, while Fe in the oxidized Fe3+ state is predominantly oxygen coordinated (estimated Fe–O bond length of approx. 2 Å), with an outer shell of Fe scatterers at approximately 3.05 Å; and (v) no significant differences occur in Cu or Fe speciation at key nodes in the apocrine cycle. Findings imply that S and B cells form integrated unit-pairs; a functional role for secretions from these cellular units in the digestion of recalcitrant dietary components is hypothesized.

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Abstract: This study presents a multifaceted approach of Zn adsorption onto dry Fucus vesiculosus originating from the Irish Sea. Metal chemistry as well as algae surface charge properties were characterized before adsorption. Zn adsorption tests were run as function of: pH, algae concentration and metal source. A comparison with Co, Cd, and Cu adsorption – in mono-ion solutions was also performed. Adsorption kinetics, fitted with pseudo-first order (PFO) and pseudo-second order (PSO) kinetic model, allowed the uptake parameters to be found and a comparison of kinetic rates. Synchrotron X-Ray-Florescence and X-Ray Absorption Spectroscopy measurements of Zn on algae after exposure permitted the extraction of direct information about Zn spatial distribution and bonding environment. The results showed that the carboxylic groups are the ones involved in the heterogeneously distributed Zn adsorption at low pH, Zn being coordinated with 5 - 6 O at bond distances varying from 1.98-2.03 Å - as in Zn alginate. Synchrotron results provide confirmation that, relative to Zn, alginate is one of the main algae components responsible for metal binding.

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Abstract: Zinc is known to play an important role in many cellular processes, and the levels of zinc are controlled by specific transporters from the ZIP (SLC39A) influx transporter group and the ZnT (SLC30A) efflux transporter group. The distribution of zinc was measured in 59 samples of invasive ductal carcinoma of breast using synchrotron radiation micro probe x-ray fluorescence facilities. The samples were formalin fixed paraffin embedded tissue micro arrays (TMAs) enabling a high throughput of samples and allowing us to correlate the distribution of trace metals with tumour cell distribution and, for the first time, important biological variables. The samples were divided into two classes, 34 oestrogen receptor positive (ER+ve) and 25 oestrogen receptor negative (ER-ve) based on quantitative immunohistochemistry assessment. The overall levels of zinc (i.e. in tumour and surrounding tissue) in the ER+ve samples were on average 60% higher than those in the ER-ve samples. The zinc levels were higher in the ER+ve tumour areas compared to the ER-ve tumour areas with the mean levels in the ER+ve samples being approximately 80% higher than the mean ER-ve levels. However, the non-tumour tissue regions of the samples contained on average the same levels of zinc in both types of breast cancers. The relative levels of zinc in tumour areas of the tissue were compared with levels in areas of non-tumour surrounding tissue. There was a significant increase in zinc in the tumour regions of the ER+ve samples compared to the surrounding regions (P < 0.001) and a non-significant increase in the ER-ve samples. When comparing the increase in zinc in the tumour regions expressed as a percentage of the surrounding non-tumour tissue zinc level in the same sample, a significant difference between the ER+ve and ER-ve samples was found (P < 0.01).

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Abstract: The chemistry of molybdenum species in artificial corrosion pits on 316L stainless steel was investigated using X-ray absorption spectroscopy (XANES). It was found that the K-edge spectra are consistent with the presence of an Mo(III) species. The presence of Mo(VI) polymolybdates as been proposed to explain the well-known beneficial effects of Mo in decreasing the susceptibility of stainless steel to localised corrosion, but no evidence of these species was found. High resolution measurements (with a spatial resolution of 3.5 μm in the vertical direction) through the dissolving metal interface did not detect the presence of any different Mo-containing species in the vicinity of the salt film. However, the spatial resolution was insufficient to detect the presence of submonolayer species on the dissolving metal surface that have been proposed to block active dissolution.

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Abstract: The imaging of catalysts and other functional materials under reaction conditions has advanced significantly in recent years. The combination of the computed tomography (CT) approach with methods such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) now enables local chemical and physical state information to be extracted from within the interiors of intact materials which are, by accident or design, inhomogeneous. In this work, we follow the phase evolution during the initial reduction step(s) to form Co metal, for Co-containing particles employed as Fischer–Tropsch synthesis (FTS) catalysts; firstly, working at small length scales (approx. micrometre spatial resolution), a combination of sample size and density allows for transmission of comparatively low energy signals enabling the recording of ‘multimodal’ tomography, i.e. simultaneous XRF–CT, XANES–CT and XRD–CT. Subsequently, we show high-energy XRD–CT can be employed to reveal extent of reduction and uniformity of crystallite size on millimetre-sized TiO2 trilobes. In both studies, the CoO phase is seen to persist or else evolve under particular operating conditions and we speculate as to why this is observed.