101 research outputs found

    Energy Level Alignment at the C60 Monolayer WS2 Interface on Insulating and Conductive Substrates

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    Combining a transition metal dichalcogenide monolayer ML and molecular semiconductors is an attractive route for forming nanoscale hybrid van der Waals heterostructures with potentially novel opto electronic properties. The energy level alignment at the hybrid interface governs these properties, but precise determination of the interfacial electronic structure is challenging due to the pronounced excitonic nature of both components and the non trivial band structure of the inorganic ML. For instance, dielectric screening by the supporting substrate of such a heterostructure may impact the energy levels, but very few experiments have attended to this important issue to date. Here, it is shown how photoelectron spectroscopy can be used to unravel the energy level line up at the C60 ML WS2 interface supported on an insulating sapphire and a semi metallic graphite substrates. On both substrates, an almost identical staggered type II level alignment is determined. However, C60 ML WS2 exhibits stronger n type characteristics on sapphire, which is suggested to be due to native donor type defects of ML WS2. While these remain occupied and active on the insulating substrate, they are emptied into the charge reservoir of the conductive substrate. These insights should be considered in the future design of functional heterostructures of inorganic ML and molecular semiconductor material

    Position locking of volatile reaction products by atmosphere and capping layers slows down photodecomposition of methylammonium lead triiodide perovskite

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    The remarkable progress of metal halide perovskites in photovoltaics has led to the power conversion efficiency approaching 26%. However, practical applications of perovskite-based solar cells are challenged by the stability issues, of which the most critical one is photo-induced degradation. Bare CH(3)NH(3)PbI(3) perovskite films are known to decompose rapidly, with methylammonium and iodine as volatile species and residual solid PbI(2) and metallic Pb, under vacuum under white light illumination, on the timescale of minutes. We find, in agreement with previous work, that the degradation is non-uniform and proceeds predominantly from the surface, and that illumination under N(2) and ambient air (relative humidity 20%) does not induce substantial degradation even after several hours. Yet, in all cases the release of iodine from the perovskite surface is directly identified by X-ray photoelectron spectroscopy. This goes in hand with a loss of organic cations and the formation of metallic Pb. When CH(3)NH(3)PbI(3) films are covered with a few nm thick organic capping layer, either charge selective or non-selective, the rapid photodecomposition process under ultrahigh vacuum is reduced by more than one order of magnitude, and becomes similar in timescale to that under N(2) or air. We conclude that the light-induced decomposition reaction of CH(3)NH(3)PbI(3), leading to volatile methylammonium and iodine, is largely reversible as long as these products are restrained from leaving the surface. This is readily achieved by ambient atmospheric pressure, as well as a thin organic capping layer even under ultrahigh vacuum. In addition to explaining the impact of gas pressure on the stability of this perovskite, our results indicate that covalently “locking” the position of perovskite components at the surface or an interface should enhance the overall photostability

    Gene expression differences in relation to age and social environment in queen and worker bumble bees

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    Eusocial insects provide special insights into the genetic pathways influencing aging because of their long-lived queens and flexible aging schedules. Using qRT-PCR in the primitively eusocial bumble bee Bombus terrestris (Linnaeus), we investigated expression levels of four candidate genes associated with taxonomically widespread age-related pathways (coenzyme Q biosynthesis protein 7, COQ7; DNA methyltransferase 3, Dnmt3; foraging, for; and vitellogenin, vg). In Experiment 1, we tested how expression changes with queen relative age and productivity. We found a significant age-related increase in COQ7 expression in queen ovary. In brain, all four genes showed higher expression with increasing female (queen plus worker) production, with this relationship strengthening as queen age increased, suggesting a link with the positive association of fecundity and longevity found in eusocial insect queens. In Experiment 2, we tested effects of relative age and social environment (worker removal) in foundress queens and effects of age and reproductive status in workers. In this experiment, workerless queens showed significantly higher for expression in brain, as predicted if downregulation of for is associated with the cessation of foraging by foundress queens following worker emergence. Workers showed a significant age-related increase in Dnmt3 expression in fat body, suggesting a novel association between aging and methylation in B. terrestris. Ovary activation was associated with significantly higher vg expression in fat body and, in younger workers, in brain, consistent with vitellogenin's ancestral role in regulating egg production. Overall, our findings reveal a mixture of novel and conserved features in age-related genetic pathways under primitive eusociality

    Ovarian germ cell tumors with rhabdomyosarcomatous components and later development of growing teratoma syndrome: a case report

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    <p>Abstract</p> <p>Introduction</p> <p>Development of a sarcomatous component in a germ cell tumor is an uncommon phenomenon. Most cases reported have a grim prognosis. Growing teratoma syndrome is also an uncommon phenomenon and occurs in approximately 2% to 7% of non seminomatous germ cell tumors and should be treated surgically.</p> <p>Case presentation</p> <p>We report the case of a 12-year-old Asian girl with an ovarian mixed germ cell tumor containing a rhabdomyosarcomatous component. She was treated with a germ cell tumor chemotherapy regimen and rhabdomyosarcoma-specific chemotherapy. Towards the end of her treatment, she developed a retroperitoneal mass that was increasing in size. It was completely resected, revealing a mature teratoma, consistent with growing teratoma syndrome. She is still in complete remission approximately three years after presentation.</p> <p>Conclusion</p> <p>The presence of rhabdomyosarcoma in a germ cell tumor should be treated by a combined chemotherapy regimen (for germ cell tumor and rhabdomyosarcoma). In addition, development of a mass during or after therapy with normal serum markers should raise the possibility of growing teratoma syndrome that should be treated surgically.</p

    The Schottky Mott Rule Expanded for Two Dimensional Semiconductors Influence of Substrate Dielectric Screening

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    A comprehensive understanding of the energy level alignment mechanisms between two dimensional 2D semiconductors and electrodes is currently lacking, but it is a prerequisite for tailoring the interface electronic properties to the requirements of device applications. Here, we use angle resolved direct and inverse photoelectron spectroscopy to unravel the key factors that determine the level alignment at interfaces between a monolayer of the prototypical 2D semiconductor MoS2 and conductor, semiconductor, and insulator substrates. For substrate work function amp; 934;sub values below 4.5 eV we find that Fermi level pinning occurs, involving electron transfer to native MoS2 gap states below the conduction band. For amp; 934;sub above 4.5 eV, vacuum level alignment prevails but the charge injection barriers do not strictly follow the changes of amp; 934;sub as expected from the Schottky Mott rule. Notably, even the trends of the injection barriers for holes and electrons are different. This is caused by the band gap renormalization of monolayer MoS2 by dielectric screening, which depends on the dielectric constant amp; 949;r of the substrate. Based on these observations, we introduce an expanded Schottky Mott rule that accounts for band gap renormalization by amp; 949;r dependent screening and show that it can accurately predict charge injection barriers for monolayer MoS2. It is proposed that the formalism of the expanded Schottky Mott rule should be universally applicable for 2D semiconductors, provided that material specific experimental benchmark data are availabl

    One pot synthesis of high capacity silicon anodes via on copper growth of a semiconducting, porous polymer

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    Silicon based anodes with lithium ions as charge carriers have the highest predicted theoretical specific capacity of 3579 mA h g amp; 8722;1 for Li15Si4 . Contemporary electrodes do not achieve this theoretical value largely because conventional production paradigms rely on the mixing of weakly coordinated components. In this paper, a semiconductive triazine based graphdiyne polymer network is grown around silicon nanoparticles directly on the current collector, a copper sheet. The porous, semiconducting organic framework 1 adheres to the current collector on which it grows via cooperative van der Waals interactions, 2 acts effectively as conductor for electrical charges and binder of silicon nanoparticles via conjugated, covalent bonds, and 3 enables selective transport of electrolyte and Li ions through pores of defined size. The resulting anode shows extraordinarily high capacity at the theoretical limit of fully lithiated silicon. Finally, we combine our anodes in proof of concept battery assemblies using a conventional layered Ni rich oxide cathod

    Macrophages Homing to Metastatic Lymph Nodes Can Be Monitored with Ultrasensitive Ferromagnetic Iron-Oxide Nanocubes and a 1.5T Clinical MR Scanner

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    Background: Due to the ability of macrophages to specifically home to tumors, their potential use as a delivery vehicle for cancer therapeutics has been suggested. Tracking the delivery and engraftment of macrophages into human tumors with a 1.5T clinical MR scanner requires the development of sensitive contrast agents for cell labeling. Therefore, this study aimed to determine whether intravenously injected macrophages could target a primary tumor as well as metastatic LNs, and whether these cells could be detected in vivo by MRI. Methodology: Peritoneal macrophages were obtained from BALB/c nude mice. The viability, phagocytotic capacity and migratory activity of the macrophages were assessed. MR imaging was performed using a clinical 1.5 T MR scanner and we estimated the T2 * of the labeled macrophages. Metastatic lymph nodes were produced in BALB/c nude mice. We administrated 2610 6 macrophages labeled with 50 mg Fe/mL FIONs intravenously into the mice. In the 3D T2 * GRE MR images obtained one day after the injection of the labeled macrophages or FION solution, the percentages of pixels in the tumors or LNs below the minimum normalized SI (signal intensity) threshold were summated and reported as the black pixel count (%) for the FION hypointensity. Tumors in the main tumor model as well as the brachial, axillary and inguinal lymph nodes in the metastatic LN models were removed and stained. For all statistical analyses, single-group data were assessed using t test or the Mann-Whitney test. Repeated measurements analysis of variance (ANOVA) with Tukey–Krame

    Inhibition of Effector Function but Not T Cell Activation and Increase in FoxP3 Expression in T Cells Differentiated in the Presence of PP14

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    Background: T-helper polarization of naïve T cells is determined by a complex mechanism that involves many factors, eventually leading to activation of Th1, Th2, or Th17 responses or alternatively the generation of regulatory T cells. Placental Protein 14 (PP14) is a 28 kDa glycoprotein highly secreted in early pregnancy that is able to desensitize T cell receptor (TCR) signaling and modulate T cell activation. Methodology/Principal Findings: Prolonged antigen-specific stimulation of T cells in the presence of PP14 resulted in an impaired secretion of IFN-c, IL-5 and IL-17 upon restimulation, although the cells proliferated and expressed activation markers. Furthermore, the generation of regulatory CD4 + CD25 high Foxp3 + T cells was induced in the presence of PP14, in both antigen-specific as well as polyclonal stimulation. In accordance with previous reports, we found that the induction of FoxP3 expression by PP14 is accompanied by down regulation of the PI3K-mTOR signaling pathway. Conclusions/Significance: These data suggest that PP14 arrests T cells in a unique activated state that is not accompanied with the acquisition of effector function, together with promoting the generation of regulatory T cells. Taken together, our results may elucidate the role of PP14 in supporting immune tolerance in pregnancy by reducing T cell effector function
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