Tailoring the performance of ZnO for oxygen evolution by effective transition metal doping

In the quest for active and inexpensive (photo)electrocatalysts, atomistic simulations of the oxygen evolution reaction (OER) are essential for understanding the catalytic process of water splitting at solid surfaces. In this paper, we study the enhancement of the OER by first-row transition-metal (TM) doping of the abundant semiconductor ZnO, using density functional theory (DFT) calculations on a substantial number of possible structures and bonding geometries. The calculated overpotential for undoped ZnO is 1.0 V. For TM dopants in the 3d series from Mn to Ni, the overpotentials decrease from 0.9 V for Mn, and 0.6 V for Fe, down to 0.4 V for Co, and rise again to 0.5 V for Ni and 0.8 eV for Cu. We analyze the overpotentials in terms of the binding to the surface of the species involved in the four reaction steps of the OER. The Gibbs free energies associated with the adsorption of these intermediate species increase down the series from Mn to Zn, but the difference between OH and OOH adsorption (the species involved in the first, respectively the third reaction step) is always in the range 3.0-3.3 eV, despite a considerable variation in possible bonding geometries. The bonding of the O intermediate species (involved in the second reaction step), which is optimal for Co, and to a somewhat lesser extend for Ni, then ultimately determines the overpotential. These results imply that both Co and Ni are promising dopants for increasing the activity of ZnO-based anodes for the OER.</p

Benchmarking the Utility of w-Event Differential Privacy Mechanisms: When Baselines Become Mighty Competitors

The w-event framework is the current standard for ensuring differential privacy on continuously monitored data streams. Following the proposition of w-event differential privacy, various mechanisms to implement the framework are proposed. Their comparability in empirical studies is vital for both practitioners to choose a suitable mechanism, and researchers to identify current limitations and propose novel mechanisms. By conducting a literature survey, we observe that the results of existing studies are hardly comparable and partially intrinsically inconsistent. To this end, we formalize an empirical study of w-event mechanisms by re-occurring elements found in our survey. We introduce requirements on these elements that ensure the comparability of experimental results. Moreover, we propose a benchmark that meets all requirements and establishes a new way to evaluate existing and newly proposed mechanisms. Conducting a large-scale empirical study, we gain valuable new insights into the strengths and weaknesses of existing mechanisms. An unexpected - yet explainable - result is a baseline supremacy, i.e., using one of the two baseline mechanisms is expected to deliver good or even the best utility. Finally, we provide guidelines for practitioners to select suitable mechanisms and improvement options for researchers

Network dynamics:a computational framework for the simulation of the glassy state

An out-of-equilibrium simulation method for tracking the time evolution of glassy systems (or any other systems that can be described by hopping dynamics over a network of discrete states) is presented. Graph theory and complexity concepts are utilised, alongside the method of the dynamical integration of a Markovian web (G. C. Boulougouris and D. N. Theodorou, J. Chem. Phys., 2007, 127, 084903) in order to provide a unified framework for dealing with the long time-scales of non-ergodic systems. Within the developed formalism, the network of states accessible to the system is considered a finite part of the overall universe, communicating with it through well-defined boundary states. The analytical solution of the probability balance equation proceeds without the need for assuming the existence of an equilibrium distribution among the states of the network and the corresponding survival and escape probabilities (as functions of time) are defined. More importantly, the study of the probability flux through the dividing surface separating the system and its environment reveals the relaxation mechanisms of the system. We apply our approach to the network of states obtained by exploring the energy landscape of an atomistically detailed glassy specimen of atactic polystyrene. The rate constants connecting different basins of the landscape are evaluated by multi-dimensional transition-state-theory. We are able to accurately probe the appearance of the δ- and γ-subglass relaxation mechanisms and their relevant time-scales, out of atomistic simulations. The proposed approach can fill a gap in the rational molecular design toolbox, by providing an alternative to molecular dynamics for structural relaxation in glasses and/or other slow molecular processes (e.g., adsorption or desorption) that involve very distant time-scales.</p

Roadmap on multiscale materials modeling

Modeling and simulation is transforming modern materials science, becoming an important tool for the discovery of new materials and material phenomena, for gaining insight into the processes that govern materials behavior, and, increasingly, for quantitative predictions that can be used as part of a design tool in full partnership with experimental synthesis and characterization. Modeling and simulation is the essential bridge from good science to good engineering, spanning from fundamental understanding of materials behavior to deliberate design of new materials technologies leveraging new properties and processes. This Roadmap presents a broad overview of the extensive impact computational modeling has had in materials science in the past few decades, and offers focused perspectives on where the path forward lies as this rapidly expanding field evolves to meet the challenges of the next few decades. The Roadmap offers perspectives on advances within disciplines as diverse as phase field methods to model mesoscale behavior and molecular dynamics methods to deduce the fundamental atomic-scale dynamical processes governing materials response, to the challenges involved in the interdisciplinary research that tackles complex materials problems where the governing phenomena span different scales of materials behavior requiring multiscale approaches. The shift from understanding fundamental materials behavior to development of quantitative approaches to explain and predict experimental observations requires advances in the methods and practice in simulations for reproducibility and reliability, and interacting with a computational ecosystem that integrates new theory development, innovative applications, and an increasingly integrated software and computational infrastructure that takes advantage of the increasingly powerful computational methods and computing hardware

Impact of chemotherapy for HIV-1 related lymphoma on residual viremia and cellular HIV-1 DNA in patients on suppressive antiretroviral therapy

The first cure of HIV-1 infection was achieved through complex, multimodal therapy including myeloablative chemotherapy, total body irradiation, anti-Thymocyte globulin, and allogeneic stem cell transplantation with a CCR5 delta32 homozygous donor. The contributions of each component of this therapy to HIV-1 eradication are unclear. To assess the impact of cytotoxic chemotherapy alone on HIV-1 persistence, we longitudinally evaluated low-level plasma viremia and HIV-1 DNA in PBMC from patients in the ACTG A5001/ALLRT cohort on suppressive antiretroviral therapy (ART) who underwent chemotherapy for HIV-1 related lymphoma without interrupting ART. Plasma HIV-1 RNA, total HIV-1 DNA and 2-LTR circles (2-LTRs) in PBMC were measured using sensitive qPCR assays. In the 9 patients who received moderately intensive chemotherapy for HIV-1 related lymphoma with uninterrupted ART, low-level plasma HIV-1 RNA did not change significantly with chemotherapy: median HIV-1 RNA was 1 copy/mL (interquartile range: 1.0 to 20) pre-chemotherapy versus 4 copies/mL (interquartile range: 1.0 to 7.0) post-chemotherapy. HIV-1 DNA levels also did not change significantly, with median prechemotherapy HIV-1 DNA of 355 copies/106 CD4+ cells versus 228 copies/106 CD4+ cells post-chemotherapy. 2-LTRs were detectable in 2 of 9 patients pre-chemotherapy and in 3 of 9 patients post-chemotherapy. In summary, moderately intensive chemotherapy for HIV-1 related lymphoma in the context of continuous ART did not have a prolonged impact on HIV-1 persistence. © 2014 Cillo et al

Informed consent for HIV cure research in South Africa: issues to consider

Background: South Africa has made great progress in the development of HIV/AIDS testing, treatment and prevention campaigns. Yet, it is clear that prevention and treatment campaigns alone are not enough to bring this epidemic under control. Discussion: News that the “Berlin patient” and the “Mississippi baby” have both been “cured” of HIV brought hope to people living with HIV/AIDS in South Africa that a cure for HIV/AIDS is within reach. Despite the recent setbacks announced in the “Mississippi Baby” case, protocols aimed at curing HIV/AIDS are being developed in South Africa. However with evidence to suggest that participants in clinical trials do not understand the basic concepts in the informed consent process, there is concern that future participants in HIV/AIDS cure research will lack comprehension of the basic elements of future clinical trials that aims to cure HIV/AIDS and confuse research with clinical care. Summary: Research ethics committees have an important role to play in ensuring that participants understand the basic concepts discussed in the informed consent process, that they understand that research is not clinical care and they are unlikely to benefit from any early phase trials seeking to cure HIV/AIDS

High correlation of the proteome patterns in bone marrow and peripheral blood blast cells in patients with acute myeloid leukemia

<p>Abstract</p> <p>Background</p> <p>When comparing myelogenous blasts from bone marrow and peripheral blood, immunophenotyping usually show a strong correlation of expression of surface antigens. However, it remains to be determined, whether this correlation also exists on the level of protein expression.</p> <p>Method</p> <p>Therefore, we investigated both bone marrow and peripheral blood blast cells from six patients with newly diagnosed acute myeloid leukemia (AML) using conventional two-dimensional electrophoresis in the first dimension and linear polyacrylamide gels (12%) in the second dimension. Proteins were visualized using the silver staining method and image analysis was performed using the PDQuest system.</p> <p>Results</p> <p>For each patient over 80 proteins were evaluated in the sample from peripheral blood and bone marrow. We could demonstrate that the protein expression profile of bone marrow did not significantly differ from the expression patterns of peripheral blast cells.</p> <p>Conclusion</p> <p>The proteome-set of leukemic blast cells from marrow and blood, does not differ substantially when drawn from AML patients with over 80 percent blast cells in both compartments. This indicates that in AML, blasts from peripheral blood samples can be considered suitable for investigations of the proteome using 2D-electrophoresis.</p