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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.

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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.

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Abstract: Iron (Fe) limits primary productivity and nitrogen fixation in large regions of the world’s oceans. Hydrothermal supply of Fe to the global deep ocean is extensive; however, most of the previous work has focused on examining high temperature, acidic, focused flow on ridge axes that create “black smoker” plumes. The contribution of other types of venting to the global ocean Fe cycle has received little attention. To thoroughly understand hydrothermal Fe sources to the ocean, different types of vent site must be compared. To examine the role of more diffuse, higher pH sources of venting, a hydrothermal plume above the Von Damm vent field (VDVF) was sampled for Total dissolvable Fe (unfiltered, TDFe), dissolved Fe (<0.2 μm, dFe) and soluble Fe (<0.02 μm, sFe). Plume particles sampled in situ were characterized using scanning electron microscopy and soft X-ray spectromicroscopy. The VDVF vents emit visibly clear fluids with particulate Fe (TDFe-dFe, >0.2 μm) concentrations up to 196 nmol kg–1 comparable to concentrations measured in black smoker plumes on the Mid-Atlantic Ridge. Colloidal Fe (cFe) and sFe increased as a fraction of TDFe with decreasing TDFe concentration. This increase in the percentage of sFe and cFe within the plume cannot be explained by settling of particulates or mixing with background seawater. The creation of new cFe and sFe within the plume from the breakdown of pFe is required to close the Fe budget. We suggest that the proportional increase in cFe and sFe reflects the entrainment, breakdown and recycling of Fe bearing organic particulates near the vents. Fe plume profiles from the VDVF differ significantly from previous studies of “black smoker” vents where formation of new pFe in the plume decreases the amount of cFe. Formation and removal of Fe-rich colloids and particles will control the amount and physico-chemical composition of dFe supplied to the deep ocean from hydrothermal systems. This study highlights the differences in the stabilization of hydrothermal Fe from an off-axis diffuse source compared to black smokers. Off-axis diffuse venting represent a potentially significant and previously overlooked Fe source to the ocean due to the difficulties in detecting and locating such sites.

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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.

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Abstract: In this paper we report on the fabrication and testing of a novel concept of electrochemical microcell for in-situ soft X-ray microspectroscopy in transmission. The microcell, fabricated by electron-beam lithography, implements an improved electrode design, with optimal current density distribution and minimised ohmic drop, allowing the same three-electrode electrochemical control achievable with traditional cells. Moreover standard electroanalytical measurements, such as cyclic voltammetry, can be routinely performed. As far as the electrolyte is concerned, we selected a room-temperature ionic-liquid. Some of the materials belonging to this class, in addition to a broad range of outstanding electrochemical properties, feature two highlights that are crucial for in situ, soft X-ray transmission work: spinnability, enabling accurate thickness control, and stability to UHV, allowing operation of an open cell in the analysis chamber vacuum (10−6 mbar). The cell can, of course, be used also with non-vacuum stable electrolytes in the sealed version developed in previous work in our group. In this study, the microcell designed, fabricated and tested in situ by applying an anodic polarisation to a Au electrode and following the formation of a distribution of corrosion features. This specific material combination presented in this work does not limit the cell concept, that can implement any electrodic material grown by lithography, any liquid electrolyte and any spinnable solid electrolyte.