The influence of intercalated oxygen on the properties of graphene on polycrystalline Cu under various environmental conditions.

Intercalation of oxygen at the interface of graphene grown by chemical vapour deposition and its polycrystalline copper catalyst can have a strong impact on the electronic, chemical and structural properties of both the graphene and the Cu. This can affect the oxidation resistance of the metal as well as subsequent graphene transfer. Here, we show, using near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), X-ray absorption near edge spectroscopy (XANES), energy dispersive X-ray spectroscopy (EDX) and (environmental) scanning electron microscopy (ESEM) that both the oxygen intercalation and de-intercalation are kinetically driven and can be clearly distinguished from carbon etching. The obtained results reveal that a charge transfer between as grown graphene and Cu can be annulled by intercalating oxygen creating quasi-free-standing graphene. This effect is found to be reversible on vacuum annealing proceeding via graphene grain boundaries and defects within the graphene but not without loss of graphene by oxidative etching for repeated (de-)intercalation cycles.P.R.K. acknowledges the Lindemann Trust Fellowship. R.S.W. acknowledges a Research Fellowship from St. John’s College, Cambridge. S.H. acknowledges funding from ERC grant InsituNANO (No. 279342) and EPSRC under grant GRAPHTED (Ref. EP/K016636/1). R.B. and A.K.-G. acknowledge funding from EU project GRAFOL, grant 285275.This is the final published version. It first appeared at http://pubs.rsc.org/en/Content/ArticleLanding/2014/CP/c4cp04025b#!divAbstract

Multi-Directional Growth of Aligned Carbon Nanotubes Over Catalyst Film Prepared by Atomic Layer Deposition

The structure of vertically aligned carbon nanotubes (CNTs) severely depends on the properties of pre-prepared catalyst films. Aiming for the preparation of precisely controlled catalyst film, atomic layer deposition (ALD) was employed to deposit uniform Fe2O3 film for the growth of CNT arrays on planar substrate surfaces as well as the curved ones. Iron acetylacetonate and ozone were introduced into the reactor alternately as precursors to realize the formation of catalyst films. By varying the deposition cycles, uniform and smooth Fe2O3 catalyst films with different thicknesses were obtained on Si/SiO2 substrate, which supported the growth of highly oriented few-walled CNT arrays. Utilizing the advantage of ALD process in coating non-planar surfaces, uniform catalyst films can also be successfully deposited onto quartz fibers. Aligned few-walled CNTs can be grafted on the quartz fibers, and they self-organized into a leaf-shaped structure due to the curved surface morphology. The growth of aligned CNTs on non-planar surfaces holds promise in constructing hierarchical CNT architectures in future

Biological strategy for the fabrication of highly ordered aragonite helices: The microstructure of the cavolinioidean gastropods

The Cavolinioidea are planktonic gastropods which construct their shells with the so-called aragonitic helical fibrous microstructure, consisting of a highly ordered arrangement of helically coiled interlocking continuous crystalline aragonite fibres. Our study reveals that, despite the high and continuous degree of interlocking between fibres, every fibre has a differentiated organic-rich thin external band, which is never invaded by neighbouring fibres. In this way, fibres avoid extinction. These intra-fibre organic-rich bands appear on the growth surface of the shell as minuscule elevations, which have to be secreted differentially by the outer mantle cells. We propose that, as the shell thickens during mineralization, fibre secretion proceeds by a mechanism of contact recognition and displacement of the tips along circular trajectories by the cells of the outer mantle surface. Given the sizes of the tips, this mechanism has to operate at the subcellular level. Accordingly, the fabrication of the helical microstructure is under strict biological control. This mechanism of fibre-by-fibre fabrication by the mantle cells is unlike that any other shell microstructure.Funding was provided by Research Projects CGL2013-48247-P of the Spanish Ministerio de Economía y Competitividad (MINECO) and Fondo Europeo de Desarrollo Regional (FEDER), and P10-RNM6433 of the Andalusian Consejería de Economía, Investigación, Ciencia y Empleo, of the Junta de Andalucía, and by the Research Group RNM363 (latter Institution)

Stabilisation of β-Catenin Downstream of T Cell Receptor Signalling

The role of TCF/β-catenin signalling in T cell development is well established, but important roles in mature T cells have only recently come to light.Here we have investigated the signalling pathways that are involved in the regulation of β-catenin in primary human T cells. We demonstrate that β-catenin expression is upregulated rapidly after T cell receptor (TCR) stimulation and that this involves protein stabilisation rather than an increase in mRNA levels. Similar to events in Wnt signalling, the increase in β-catenin coincides with an inhibition of GSK3, the kinase that is required for β-catenin degradation. β-catenin stabilisation in T cells can also be induced by the activation of PKC with phorbol esters and is blocked by inhibitors of phosphatidylinositol 3-kinase (PI3K) and phospholipase C (PKC). Upon TCR signalling, β-catenin accumulates in the nucleus and, parallel to this, the ratio of TCF1 isoforms is shifted in favour of the longer β-catenin binding isoforms. However, phosphorylated β-catenin, which is believed to be inactive, can also be detected and the expression of Wnt target genes Axin2 and dickkopf is down regulated.These data show that in mature human T cells, TCR signalling via PI3K and PKC can result in the stabilisation of β-catenin, allowing β-catenin to migrate to the nucleus. They further highlight important differences between β-catenin activities in TCR and Wnt signalling

Thermally stable single atom Pt/m-Al2O3 for selective hydrogenation and CO oxidation

Single-atom metal catalysts offer a promising way to utilize precious noble metal elements more effectively, provided that they are catalytically active and sufficiently stable. Herein, we report a synthetic strategy for Pt single-atom catalysts with outstanding stability in several reactions under demanding conditions. The Pt atoms are firmly anchored in the internal surface of mesoporous Al2O3, likely stabilized by coordinatively unsaturated pentahedral Al3+ centres. The catalyst keeps its structural integrity and excellent performance for the selective hydrogenation of 1,3-butadiene after exposure to a reductive atmosphere at 200 °C for 24 h. Compared to commercial Pt nanoparticle catalyst on Al2O3 and control samples, this system exhibits significantly enhanced stability and performance for n-hexane hydro-reforming at 550 °C for 48 h, although agglomeration of Pt single-atoms into clusters is observed after reaction. In CO oxidation, the Pt single-atom identity was fully maintained after 60 cycles between 100 and 400 °C over a one-month period

Antibody Repertoires in Humanized NOD-scid-IL2Rγnull Mice and Human B Cells Reveals Human-Like Diversification and Tolerance Checkpoints in the Mouse

Immunodeficient mice reconstituted with human hematopoietic stem cells enable the in vivo study of human hematopoiesis. In particular, NOD-scid-IL2Rγnull engrafted mice have been shown to have reasonable levels of T and B cell repopulation and can mount T-cell dependent responses; however, antigen-specific B-cell responses in this model are generally poor. We explored whether developmental defects in the immunoglobulin gene repertoire might be partly responsible for the low level of antibody responses in this model. Roche 454 sequencing was used to obtain over 685,000 reads from cDNA encoding immunoglobulin heavy (IGH) and light (IGK and IGL) genes isolated from immature, naïve, or total splenic B cells in engrafted NOD-scid-IL2Rγnull mice, and compared with over 940,000 reads from peripheral B cells of two healthy volunteers. We find that while naïve B-cell repertoires in humanized mice are chiefly indistinguishable from those in human blood B cells, and display highly correlated patterns of immunoglobulin gene segment use, the complementarity-determining region H3 (CDR-H3) repertoires are nevertheless extremely diverse and are specific for each individual. Despite this diversity, preferential DH-JH pairings repeatedly occur within the CDR-H3 interval that are strikingly similar across all repertoires examined, implying a genetic constraint imposed on repertoire generation. Moreover, CDR-H3 length, charged amino-acid content, and hydropathy are indistinguishable between humans and humanized mice, with no evidence of global autoimmune signatures. Importantly, however, a statistically greater usage of the inherently autoreactive IGHV4-34 and IGKV4-1 genes was observed in the newly formed immature B cells relative to naïve B or total splenic B cells in the humanized mice, a finding consistent with the deletion of autoreactive B cells in humans. Overall, our results provide evidence that key features of the primary repertoire are shaped by genetic factors intrinsic to human B cells and are principally unaltered by differences between mouse and human stromal microenvironments

A perspective on SIDS pathogenesis. The hypotheses: plausibility and evidence

Several theories of the underlying mechanisms of Sudden Infant Death Syndrome (SIDS) have been proposed. These theories have born relatively narrow beach-head research programs attracting generous research funding sustained for many years at expense to the public purse. This perspective endeavors to critically examine the evidence and bases of these theories and determine their plausibility; and questions whether or not a safe and reasoned hypothesis lies at their foundation. The Opinion sets specific criteria by asking the following questions: 1. Does the hypothesis take into account the key pathological findings in SIDS? 2. Is the hypothesis congruent with the key epidemiological risk factors? 3. Does it link 1 and 2? Falling short of any one of these answers, by inference, would imply insufficient grounds for a sustainable hypothesis. Some of the hypotheses overlap, for instance, notional respiratory failure may encompass apnea, prone sleep position, and asphyxia which may be seen to be linked to co-sleeping. For the purposes of this paper, each element will be assessed on the above criteria

Mechanism of electrochemical deposition and coloration of electrochromic V2O5 nano thin film: An in situ x-ray spectroscopy study

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Correction to: The Role of Adsorbed and Subsurface Carbon Species for the Selective Alkyne Hydrogenation Over a Pd-Black Catalyst: An Operando Study of Bulk and Surface (Topics in Catalysis, (2018), 61, 20, (2052-2061), 10.1007/s11244-018-1071-6)

The original version of this article unfortunately contained an error. The authors would like to correct the error with this erratum. In Fig. 5 the process C and B were incorrectly labelled. The corrected Fig. 5 with the right labelling is included in this erratum

The Role of Adsorbed and Subsurface Carbon Species for the Selective Alkyne Hydrogenation Over a Pd-Black Catalyst: An Operando Study of Bulk and Surface

The selective hydrogenation of propyne over a Pd-black model catalyst was investigated under operando conditions at 1 bar making use of advanced X-ray diffraction (bulk sensitive) and photo-electron spectroscopy (surface sensitive) techniques. It was found that the population of subsurface species controls the selective catalytic semi-hydrogenation of propyne to propylene due to the formation of surface and near-surface PdCx that inhibits the participation of more reactive bulk hydrogen in the hydrogenation reaction. However, increasing the partial pressure of hydrogen reduces the population of PdCx with the concomitant formation of a β-PdHx phase up to the surface, which is accompanied by a lattice expansion, allowing the participation of more active bulk hydrogen which is responsible for the unselective total alkyne hydrogenation. Therefore, controlling the surface and subsurface catalyst chemistry is crucial to control the selective alkyne semi-hydrogenation