Cross-comparison of last glacial radiocarbon and OSL ages using periglacial fan deposits

Two cores from a Weichselian periglacial alluvial fan were dated using 14C and OSL, to verify the reliability of both methods and check the upper dating limit of the 14C method. Both dating methods yielded a similar chronology for core Eerbeek-I, with infinite 14C dates for the lower part where OSL dates indicated ages of over 45 ka. Finite 14C dates were obtained throughout the core for Eerbeek-II, despite stratigraphic and OSL evidence suggesting ages beyond 14C limits. Apparently, additional chemical pre-treatment to remove younger carbon fractions did not work adequately for samples from this core. We hypothesize that this may be related to a larger influence of younger-age humin fractions in the mainly sandy Eerbeek-II deposits compared to those buffered by a thick peat layer of Eerbeek-I. We suggest that (local) stratigraphy, percolation and humification processes may impact 14C ages of organic deposits more than commonly assumed, and should receive more attention. In addition, we introduce a new method to assess robustness and validity of OSL dates and demonstrate the applicability of OSL dating methods in this setting. Our results highlight that the 14C method requires additional verification methods, such as OSL, for deposits older than 30 ka

A Three Dimensional Analysis of Au-Silica Core-Shell Nanoparticles Using Medium Energy Ion Scattering

The medium energy ion scattering (MEIS) facility at the IIAA Huddersfield has been used for the analysis of a monolayer of Au-silica core-shell nanoparticles deposited on Si substrate. Both spherical and rod shape particles were investigated and the spectra produced by 100 keV He+ ions scattered through angles of 90º and 125º were compared with the results of RBS-MAST [1] simulations performed on artificial 3D model cells containing the nanoparticles. The thickness of the silica shell, the diameter of the Au spheres, and the diameter and length of the Au nano-rods were determined from best fits of the measured set of MEIS spectra. In addition, the effect of ion irradiation on the silica shell and gold core was monitored by MEIS measurements in conjunction with RBS-MAST simulations. Ion bombardment was performed under largely different conditions, i.e., by 30 keV Ar+, 150 keV Fe+, or 2.8 MeV N+ ions in the dose range of 2×1015 - 2×1016 cm-2. Significant changes in the particle geometry can be observed due to ion beam-induced sputtering and recoil effects, the significance of which was estimated from full-cascade SRIM simulations. Rutherford backscattering spectrometry (RBS), Field emission scanning electron microscopy (FESEM), and Atomic Force Microscopy (AFM) techniques have been applied as complementary characterization tools to monitor the amount of gold and surface morphology on the un-irradiated and irradiated sample areas. We show that MEIS can yield spatial information on the geometrical changes of particulate systems at the nanometre scale

Combining dynamic modelling codes with medium energy ion scattering measurements to characterise plasma doping

Plasma doping ion implantation (PLAD) is becoming increasingly important in the manufacture of advanced semiconductor device structures but a fundamental understanding of PLAD is complicated. A model of PLAD into planar substrates has been constructed using the one dimensional computer code TRIDYN to predict collision cascades and hence substrate compositional changes during implantation. Medium Energy Ion Scattering (MEIS) measurements of dopant profiles in PLAD processed samples were used to calibrate the input ion and neutral fluxes to the model. Rules could then be proposed for how post implant profiles should be modified by a cleaning step. This learning was applied to a three dimensional TRI3DYN based model for PLAD implants into FinFET like structures. Comparison of the model to dopant profile measurements made by time of flight (TOF)-MEIS revealed the angular distributions of neutral species and doping mechanisms acting in three dimensional structures

Understanding the passivation layer formed by tolyltriazole on copper, bronze, and brass surfaces

Funding: Lubrizol Ltd is acknowledged for funding and supplying TTAH. EPSRC is acknowledged (EP/L017008/1, EP/T019298/1, and EP/R023751/1) for electron microscopy.Tolyltriazole (TTAH) is used industrially as a corrosion inhibitor for copper alloys, particularly in organic media. In this study, the morphology and chemistry of the layer formed by TTAH on copper and copper alloys under realistic conditions is investigated, with focus on the effects due to the presence of tin or zinc in the substrates. A combination of X-ray photoelectron spectroscopy (XPS), medium energy ion scattering (MEIS), and scanning transmission electron microscopy (STEM) has been used. It was found that an inhomogeneous metal–organic layer forms on the surface of copper specimens, likely in the form of copper nanoparticles surrounded by CuxTTAy complexes. This layer increases in thickness for at least 30 days. Chemically, the copper species in the layer are initially in the +2 oxidation state, but after longer exposure to TTAH, mostly Cu(I) is observed. In bronze samples, tin does not appear to segregate to the surface layer. In brass samples, zinc is depleted from the bulk and forms a thicker ZnxTTAy layer.Peer reviewe

Thermal behaviour of Cu and Au nanoparticles grown on CeO2 thin films

RM and FG acknowledge funding from EPSRC grants (RM: EP/506631/1; FG: EP/M029077/1). JAvdB and AKR acknowledge the EPSRC funding for the use of the MEIS facility at the University of Huddersfield within grant EP/M029077/1. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior -Brasil (CAPES) - Finance Code 001, by Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), and PRONEX-FAPERGS16/2551-0000479-0.Bimetallic catalysts are often more active and/or selective than their monometallic counterparts. The behaviour of such catalysts is frequently strongly dependent on the molar ratio of the two elements as well as nanoparticle size and the interaction with the support material. X-ray photoelectron spectroscopy (XPS) is an excellent surface analytical technique for probing the electronic properties of catalytic systems. When a mixture of pure and alloyed particles is present, it is more difficult to extract information from XPS given that it is a spatial averaging technique. Recently, the technique of medium energy ion scattering (MEIS) has been exploited to investigate the depth-dependent composition of nanoparticles on planar surfaces. Herein, we combine the two techniques to investigate the nature of Cu and Au nanoparticles deposited onto ultrathin CeO2 films on Si(111) examining their morphology and chemical composition as a function of annealing temperature for samples that have been maintained in an ultrahigh vacuum environment and exposed to air. The Cu/Au/CeO2/Si(111) is chosen as a model system in order to provide insight into how the catalytic properties of Cu/Au/CeO2 depend on the presence of discrete Cu and Au particles versus fully intermixed Cu/Au systems.PostprintPeer reviewe

Optical and structural characterization of Ge clusters embedded in ZrO2

The change of optical and structural properties of Ge nanoclusters in ZrO2 matrix have been investigated by spectroscopic ellipsometry versus annealing temperatures. Radio-frequency top-down magnetron sputtering approach was used to produce the samples of different types, i.e. single-layers of pure Ge, pure ZrO2 and Ge-rich-ZrO2 as well as multi-layers stacked of 40 periods of 5-nm-Ge-rich-ZrO2 layers alternated by 5-nm-ZrO2 ones. Germanium nanoclusters in ZrO2 host were formed by rapid-thermal annealing at 600-800 ∘C during 30 s in nitrogen atmosphere. Reference optical properties for pure ZrO2 and pure Ge have been extracted using single-layer samples. As-deposited multi-layer structures can be perfectly modeled using the effective medium theory. However, annealed multi-layers demonstrated a significant diffusion of elements that was confirmed by medium energy ion scattering measurements. This fact prevents fitting of such annealed structure either by homogeneous or by periodic multi-layer model

Temperature‐Dependent Re‐alignment of the Short Multifunctional Peptide BP100 in Membranes Revealed by Solid‐State NMR Spectroscopy and Molecular Dynamics Simulations

BP100 is a cationic undecamer peptide with antimicrobial and cell-penetrating activities. The orientation of this amphiphilic α-helix in lipid bilayers was examined under numerous conditions using solid-state 19F, 15N and 2H NMR. At high temperatures in saturated phosphatidylcholine lipids, BP100 lies flat on the membrane surface, as expected. Upon lowering the temperature towards the lipid phase transition, the helix is found to flip into an upright transmembrane orientation. In thin bilayers, this inserted state was stable at low peptide concentration, but thicker membranes required higher peptide concentrations. In the presence of lysolipids, the inserted state prevailed even at high temperature. Molecular dynamics simulations suggest that BP100 monomer insertion can be stabilized by snorkeling lysine side chains. These results demonstrate that even a very short helix like BP100 can span (and thereby penetrate through) a cellular membrane under suitable conditions

Adaptive evolution of drug targets in producer and non-producer organisms

Mycophenolic acid (MPA) is an immunosuppressive drug produced by several fungi in Penicillium subgenus Penicillium. This toxic metabolite is an inhibitor of IMP dehydrogenase (IMPDH). The MPA biosynthetic cluster of P. brevicompactum contains a gene encoding a B-type IMPDH, IMPDH-B, which confers MPA-resistance. Surprisingly, all members of subgenus Penicillium contain genes encoding IMPDHs of both the A and B type, regardless of their ability to produce MPA. Duplication of the IMPDH gene occurred prior to and independent of the acquisition of the MPA biosynthetic cluster. Both P. brevicompactum IMPDHs are MPA-resistant while the IMPDHs from a nonproducer are MPA-sensitive. Resistance comes with a catalytic cost: while P. brevicompactum IMPDH-B is >1000-fold more resistant to MPA than a typical eukaryotic IMPDH, its value of k(cat)/K(m) is 0.5% of “normal”. Curiously, IMPDH-B of Penicillium chrysogenum, which does not produce MPA, is also a very poor enzyme. The MPA binding site is completely conserved among sensitive and resistant IMPDHs. Mutational analysis shows that the C-terminal segment is a major structural determinant of resistance. These observations suggest that the duplication of the IMPDH gene in Pencillium subgenus Penicillium was permissive for MPA production and that MPA production created a selective pressure on IMPDH evolution. Perhaps MPA production rescued IMPDH-B from deleterious genetic drift

Decreased TNF-α synthesis by macrophages restricts cutaneous immunosurveillance by memory CD4+ T cells during aging

Immunity declines during aging, however the mechanisms involved in this decline are not known. In this study, we show that cutaneous delayed type hypersensitivity (DTH) responses to recall antigens are significantly decreased in older individuals. However, this is not related to CC chemokine receptor 4, cutaneous lymphocyte-associated antigen, or CD11a expression by CD4+ T cells or their physical capacity for migration. Instead, there is defective activation of dermal blood vessels in older subject that results from decreased TNF-α secretion by macrophages. This prevents memory T cell entry into the skin after antigen challenge. However, isolated cutaneous macrophages from these subjects can be induced to secrete TNF-α after stimulation with Toll-like receptor (TLR) 1/2 or TLR 4 ligands in vitro, indicating that the defect is reversible. The decreased conditioning of tissue microenvironments by macrophage-derived cytokines may therefore lead to defective immunosurveillance by memory T cells. This may be a predisposing factor for the development of malignancy and infection in the skin during aging