Sulfur-Modulated Tin Sites Enable Highly Selective Electrochemical Reduction of CO2 to Formate

Electrochemical reduction of carbon dioxide (CO2RR) to formate provides an avenue to the synthesis of value-added carbon-based fuels and feedstocks powered using renewable electricity. Here, we hypothesized that the presence of sulfur atoms in the catalyst surface could promote undercoordinated sites, and thereby improve the electrochemical reduction of CO2 to formate. We explored, using density functional theory, how the incorporation of sulfur into tin may favor formate generation. We used atomic layer deposition of SnSx followed by a reduction process to synthesize sulfur-modulated tin (Sn(S)) catalysts. X-ray absorption near-edge structure (XANES) studies reveal higher oxidation states in Sn(S) compared with that of tin in Sn nanoparticles. Sn(S)/Au accelerates CO2RR at geometric current densities of 55 mA cm−2 at −0.75 V versus reversible hydrogen electrode with a Faradaic efficiency of 93%. Furthermore, Sn(S) catalysts show excellent stability without deactivation (<2% productivity change) following more than 40 hours of operation. With rapid advances in the efficient and cost-effective conversion of sunlight to electrical power, the development of storage technologies for renewable energy is even more urgent. Using renewable electricity to convert CO2 into formate simultaneously addresses the need for storage of intermittent renewable energy sources and the need to reduce greenhouse gas emissions. We report an increase of greater than 4-fold in the current density (hence the rate of reaction) in formate electrosynthesis compared with relevant controls. Our catalysts also show excellent stability without deactivation (<2% productivity change) following more than 40 hours of operation. The electrochemical reduction of carbon dioxide (CO2RR) offers a compelling route to energy storage and high-value chemical manufacture. The presence of sulfur atoms in catalyst surfaces promotes undercoordinated sites, thereby improving the electrochemical reduction of CO2 to formate. The resulting sulfur-modulated tin catalysts accelerate CO2RR at geometric current densities of 55 mA cm−2 at −0.75 V versus RHE with a Faradaic efficiency of 93%

PyClaw: Accessible, Extensible, Scalable Tools for Wave Propagation Problems

Development of scientific software involves tradeoffs between ease of use, generality, and performance. We describe the design of a general hyperbolic PDE solver that can be operated with the convenience of MATLAB yet achieves efficiency near that of hand-coded Fortran and scales to the largest supercomputers. This is achieved by using Python for most of the code while employing automatically-wrapped Fortran kernels for computationally intensive routines, and using Python bindings to interface with a parallel computing library and other numerical packages. The software described here is PyClaw, a Python-based structured grid solver for general systems of hyperbolic PDEs \cite{pyclaw}. PyClaw provides a powerful and intuitive interface to the algorithms of the existing Fortran codes Clawpack and SharpClaw, simplifying code development and use while providing massive parallelism and scalable solvers via the PETSc library. The package is further augmented by use of PyWENO for generation of efficient high-order weighted essentially non-oscillatory reconstruction code. The simplicity, capability, and performance of this approach are demonstrated through application to example problems in shallow water flow, compressible flow and elasticity

Causal Effects of the Timing of Life-course Events Age at Retirement and Subsequent Health

In this article, we combine the extensive literature on the analysis of life-course trajectories as sequences with the literature on causal inference and propose a new matching approach to investigate the causal effect of the timing of life-course events on subsequent outcomes. Our matching approach takes into account pre-event confounders that are both time-independent and time-dependent as well as life-course trajectories. After matching, treated and control individuals can be compared using standard statistical tests or regression models. We apply our approach to the study of the consequences of the age at retirement on subsequent health outcomes, using a unique data set from Swedish administrative registers. Once selectivity in the timing of retirement is taken into account, effects on hospitalization are small, while early retirement has negative effects on survival. Our approach also allows for heterogeneous treatment effects. We show that the effects of early retirement differ according to preretirement income, with higher income individuals tending to benefit from early retirement, while the opposite is true for individuals with lower income

A survey of performance enhancement of transmission control protocol (TCP) in wireless ad hoc networks

This Article is provided by the Brunel Open Access Publishing Fund - Copyright @ 2011 Springer OpenTransmission control protocol (TCP), which provides reliable end-to-end data delivery, performs well in traditional wired network environments, while in wireless ad hoc networks, it does not perform well. Compared to wired networks, wireless ad hoc networks have some specific characteristics such as node mobility and a shared medium. Owing to these specific characteristics of wireless ad hoc networks, TCP faces particular problems with, for example, route failure, channel contention and high bit error rates. These factors are responsible for the performance degradation of TCP in wireless ad hoc networks. The research community has produced a wide range of proposals to improve the performance of TCP in wireless ad hoc networks. This article presents a survey of these proposals (approaches). A classification of TCP improvement proposals for wireless ad hoc networks is presented, which makes it easy to compare the proposals falling under the same category. Tables which summarize the approaches for quick overview are provided. Possible directions for further improvements in this area are suggested in the conclusions. The aim of the article is to enable the reader to quickly acquire an overview of the state of TCP in wireless ad hoc networks.This study is partly funded by Kohat University of Science & Technology (KUST), Pakistan, and the Higher Education Commission, Pakistan

Parasitism by the Endoparasitoid, Cotesia flavipes Induces Cellular Immunosuppression and Enhances Susceptibility of the Sugar Cane Borer, Diatraea saccharalis to Bacillus thuringiensis

Cotesia flavipes Cameron (Hymenoptera: Braconidae), is a gregarious larval endoparasitoid of the sugarcane borer, Diatraea saccharalis Fabricius (Lepidoptera: Crambidae). The aim of this research was to analyze cellular immunosuppression of D. saccharalis parasitized by C. flavipes in terms of encapsulation, melanization, and hemocyte nodule formation. The encapsulation assay was done 1 and 6 days after parasitoid oviposition. In addition, the susceptibility of parasitized and nonparasitzed larvae to Bacillus thuringiensis HD 73 strain was assessed. 3, 12, and 24 h after bead injection; the percentages of encapsulation were significantly higher in unparasitized larvae compared to larvae parasitized 1 and 6 days after oviposition. Interestingly, there was a significant reduction in numbers of beads encapsulated at 1 day after oviposition compared to 6 days, and unparasitized larvae. The percentage of melanized beads decreased significantly in parasitized larvae compared to control. There was a reduction in the number of nodules in parasitized larvae compared to unparasitized controls. Larvae that were injected with polyndavirus 24 h before beads were injected showed significantly reduced encapsulation responses relative to control larvae. The D. saccharalis parasitized by C. flavipes exhibited higher susceptibility to B. thuringiensis. These results suggest that parasitization induced host immunosuppression, and the immunosuppression factors could impair the defense capacity against microbial pathogens - causing an increase in pathogen susceptibility

Genome Instability and Transcription Elongation Impairment in Human Cells Depleted of THO/TREX

THO/TREX connects transcription with genome integrity in yeast, but a role of mammalian THO in these processes is uncertain, which suggests a differential implication of mRNP biogenesis factors in genome integrity in yeast and humans. We show that human THO depletion impairs transcription elongation and mRNA export and increases instability associated with DNA breaks, leading to hyper-recombination and γH2AX and 53BP1 foci accumulation. This is accompanied by replication alteration as determined by DNA combing. Genome instability is R-loop–dependent, as deduced from the ability of the AID enzyme to increase DNA damage and of RNaseH to reduce it, or from the enhancement of R-loop–dependent class-switching caused by THOC1-depletion in CH12 murine cells. Therefore, mammalian THO prevents R-loop formation and has a role in genome dynamics and function consistent with an evolutionary conservation of the functional connection between these mRNP biogenesis factors and genome integrity that had not been anticipated

Immunotherapy moves to the early-stage setting in non-small cell lung cancer: emerging evidence and the role of biomarkers

Despite numerous advances in targeted therapy and immunotherapy in the last decade, lung cancer continues to present the highest mortality rate of all cancers. Targeted therapy based on specific genomic alterations, together with PD-1 and CTLA-4 axis blocking-based immunotherapy, have significantly improved survival in advanced non-small cell lung cancer (NSCLC) and both therapies are now well-established in this clinical setting. However, it is time for immunotherapy to be applied in patients with early-stage disease, which would be an important qualitative leap in the treatment of lung cancer patients with curative intent. Preliminary data from a multitude of studies are highly promising, but therapeutic decision-making should be guided by an understanding of the molecular features of the tumour and host. In the present review, we discuss the most recently published studies and ongoing clinical trials, controversies, future challenges and the role of biomarkers in the selection of best therapeutic options

On the Spiral Structure of the Milky Way Galaxy

We consider the possible pattern of the overall spiral structure of the Galaxy, using data on the distribution of neutral (atomic), molecular, and ionized hydrogen, on the base of the hypothesis of the spiral structure being symmetric, i.e. the assumption that spiral arms are translated into each other for a rotation around the galactic center by 180{\deg} (a two-arm pattern) or by 90{\deg} (a four-arm pattern). We demonstrate that, for the inner region, the observations are best represented with a four-arm scheme of the spiral pattern, associated with all-Galaxy spiral density waves. The basic position is that of the Carina arm, reliably determined from distances to HII regions and from HI and H2 radial velocities. This pattern is continued in the quadrants III and IV with weak outer HI arms; from their morphology, the Galaxy should be considered an asymmetric multi-arm spiral. The kneed shape of the outer arms that consist of straight segments can indicate that these arms are transient formations that appeared due to a gravitational instability in the gas disk. The distances between HI superclouds in the two arms that are the brightest in neutral hydrogen, the Carina arm and the Cygnus (Outer) arm, concentrate to two values, permitting to assume the presence of a regular magnetic field in these arms.Comment: 21 pages, 14 fugures; accepted for publication in Astronomichesky Journal (Astron. Rep.

Letter processing and font information during reading: beyond distinctiveness, where vision meets design

Letter identification is a critical front end of the reading process. In general, conceptualizations of the identification process have emphasized arbitrary sets of distinctive features. However, a richer view of letter processing incorporates principles from the field of type design, including an emphasis on uniformities across letters within a font. The importance of uniformities is supported by a small body of research indicating that consistency of font increases letter identification efficiency. We review design concepts and the relevant literature, with the goal of stimulating further thinking about letter processing during reading