Evidence To Challenge the Universality of the Horiuti-Polanyi Mechanism for Hydrogenation in Heterogeneous Catalysis:Origin and Trend of the Preference of a Non-Horiuti-Polanyi Mechanism

The Horiuti-Polanyi mechanism has been considered to be universal for explaining the mechanisms of hydrogenation reactions in heterogeneous catalysis for several decades. In this work, we examine this mechanism for the hydrogenation of acrolein, the simplest alpha,beta-unsaturated aldehyde, in gold-based systems as well as some other metals using extensive first-principles calculations. It is found that a non-Horiuti-Polanyi mechanism is favored in some cases. Furthermore, the physical origin and trend of this mechanism are revealed and discussed regarding the geometrical and electronic effects, which will have a significant influence on current understandings on heterogeneous catalytic hydrogenation reactions and the future catalyst design for these reactions.

An understanding and implications of the coverage of surface free sites in heterogeneous catalysis

The crucial roles of the coverage of surface free sites in determining catalytic activity trend are quantitatively addressed with the help of density functional theory and microkinetics. First, by analyzing activity trends of NO oxidation catalyzed by Ru, Rh, Pd, Os, Ir, and Pt surfaces with full kinetic considerations, we identify that the activity trend is in general determined by the competition between the reaction barrier and the coverage of surface free sites. Second, since the dissociation of many important molecules, such as the dissociation of N(2), O(2), and CO, follows the same Bronsted-Evans-Polanyi relationship, the coverage of surface free sites is usually a decisive term that affects the overall activity. Third, an equation is derived for the coverage of surface free sites and it is found that the coverage of surface free sites contains not only all the key thermodynamic parameters but also all the kinetic properties in the catalytic system. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3140202]

A silent witness? Medieval urban landscapes and unfolding their mapping histories

This paper offers a critical reflection on the place of maps in writing medieval urban histories. Using findings from recent research on medieval Swansea, the case is made that mapping provides an interpretative space for exploring alternative narratives about past places. To do so the paper draws upon current critical debates on cartography, particularly the idea that mapping is fluid and iterative, to suggest that Swansea's medieval urban origins are open to a range of alternative interpretations. This approach to mapping differs from that often used by historians to map medieval urban landscapes, where historic maps are simply used as ‘sources’, and the landscapes they represent used as ‘witnesses’ to past events, for creating maps, both through digital and analogue media, instead opens up – or unfolds – a landscape's past. The paper uses past attempts to map medieval Swansea to highlight difficulties in interpreting its urban landscape features, and uses multiple mappings of the medieval townscape, resulting from recent research, to question how far any sources about the past really provide a coherent narrative. Instead, multiple mappings of the medieval urban landscape – reflecting different and competing perspectives – are more attuned with how places were perceived and understood during the Middle Ages.

Religious Nationalism and Christian Zionist Pilgrimages to Holy Landscapes

The mitochondrial and autosomal mutation landscapes of prostate cancer

BACKGROUND: Prostate cancer (PCa) is the most common cancer in men. PCa is strongly age associated; low death rates in surveillance cohorts call into question the widespread use of surgery, which leads to overtreatment and a reduction in quality of life. There is a great need to increase the understanding of tumor characteristics in the context of disease progression.

OBJECTIVE: To perform the first multigenome investigation of PCa through analysis of both autosomal and mitochondrial DNA, and to integrate exome sequencing data, and RNA sequencing and copy-number alteration (CNA) data to investigate how various different tumor characteristics, commonly analyzed separately, are interconnected.

DESIGN, SETTING, AND PARTICIPANTS: Exome sequencing was applied to 64 tumor samples from 55 PCa patients with varying stage and grade. Integrated analysis was performed on a core set of 50 tumors from which exome sequencing, CNA, and RNA sequencing data were available.

OUTCOME MEASUREMENTS AND STATISTICAL ANALYSIS: Genes, mutated at a significantly higher rate relative to a genomic background, were identified. In addition, mitochondrial and autosomal mutation rates were correlated to CNAs and proliferation, assessed as a cell cycle gene expression signature.

RESULTS AND LIMITATIONS: Genes not previously reported to be significantly mutated in PCa, such as cell division cycle 27 homolog (Saccharomyces cerevisiae) (CDC27), myeloid/lymphoid or mixed-lineage leukemia 3 (MLL3), lysine (K)-specific demethylase 6A (KDM6A), and kinesin family member 5A (KIF5A) were identified. The mutation rate in the mitochondrial genome was 55 times higher than that of the autosomes. Multilevel analysis demonstrated a tight correlation between high reactive-oxygen exposure, chromosomal damage, high proliferation, and in parallel, a transition from multiclonal indolent primary PCa to monoclonal aggressive disease. As we only performed targeted sequence analysis; copy-number neutral rearrangements recently described for PCa were not accounted for.

CONCLUSIONS: The mitochondrial genome displays an elevated mutation rate compared to the autosomal chromosomes. By integrated analysis, we demonstrated that different tumor characteristics are interconnected, providing an increased understanding of PCa etiology.

Who Knows What's Going On? Mapping New Security Landscapes in Contemporary Espionage Fiction

This article explores whether or to what extent the contemporary espionage novel is able to map and interrogate transformations in the post-9/11security environment. It asks how well a form or genre of writing, typically handcuffed to the machinations and demands of the Cold War and state sovereignty, is able to adapt to a new security environment characterized by strategies of “risk assessment” and “resilience-building” and by modes or regimes of power not reducible to, or wholly controlled by, the state. In doing so, it thinks about the capacities of this type of fiction for “resisting” the formations of power it wants to make visible and is partly complicit with.

Some Attempts in the Rational Design of Heterogeneous Catalysts Using Density Functional Theory Calculations

Heterogeneous catalysis is of great importance both industrially and academically. Rational design of heterogeneous catalysts is highly desirable, and the computational screening and design method is one of the most promising approaches for rational design of heterogeneous catalysts. Herein, we review some attempts towards the rational catalyst design using density functional theory from our group. Some general relationships and theories on the activity and selectivity are covered, such as the Brønsted–Evans–Polanyi relation, volcano curves/surfaces, chemical potentials, optimal adsorption energy window and energy descriptor of selectivity. Furthermore, the relations of these relationships and theories to the rational design are discussed, and some examples of computational screening and design method are given.

Heterogeneous error-resilient scheme for spectral analysis in ultra-low power wearable electrocardiogram devices

Wearable devices performing advanced bio-signal analysis algorithms are aimed to foster a revolution in healthcare provision of chronic cardiac diseases. In this context, energy efficiency is of paramount importance, as long-term monitoring must be ensured while relying on a tiny power source. Operating at a scaled supply voltage, just above the threshold voltage, effectively helps in saving substantial energy, but it makes circuits, and especially memories, more prone to errors, threatening the correct execution of algorithms. The use of error detection and correction codes may help to protect the entire memory content, however it incurs in large area and energy overheads which may not be compatible with the tight energy budgets of wearable systems. To cope with this challenge, in this paper we propose to limit the overhead of traditional schemes by selectively detecting and correcting errors only in data highly impacting the end-to-end quality of service of ultra-low power wearable electrocardiogram (ECG) devices. This partition adopts the protection of either significant words or significant bits of each data element, according to the application characteristics (statistical properties of the data in the application buffers), and its impact in determining the output. The proposed heterogeneous error protection scheme in real ECG signals allows substantial energy savings (11% in wearable devices) compared to state-of-the-art approaches, like ECC, in which the whole memory is protected against errors. At the same time, it also results in negligible output quality degradation in the evaluated power spectrum analysis application of ECG signals.

The VINEYARD Approach: Versatile, Integrated, Accelerator-Based, Heterogeneous Data Centres.

Emerging web applications like cloud computing, Big Data and social networks have created the need for powerful centres hosting hundreds of thousands of servers. Currently, the data centres are based on general purpose processors that provide high flexibility buts lack the energy efficiency of customized accelerators. VINEYARD aims to develop an integrated platform for energy-efficient data centres based on new servers with novel, coarse-grain and fine-grain, programmable hardware accelerators. It will, also, build a high-level programming framework for allowing end-users to seamlessly utilize these accelerators in heterogeneous computing systems by employing typical data-centre programming frameworks (e.g. MapReduce, Storm, Spark, etc.). This programming framework will, further, allow the hardware accelerators to be swapped in and out of the heterogeneous infrastructure so as to offer high flexibility and energy efficiency. VINEYARD will foster the expansion of the soft-IP core industry, currently limited in the embedded systems, to the data-centre market. VINEYARD plans to demonstrate the advantages of its approach in three real use-cases (a) a bio-informatics application for high-accuracy brain modeling, (b) two critical financial applications, and (c) a big-data analysis application.

A Scalable Runtime for the ECOSCALE Heterogeneous Exascale Hardware Platform

Exascale computation is the next target of high performance computing. In the push to create exascale computing platforms, simply increasing the number of hardware devices is not an acceptable option given the limitations of power consumption, heat dissipation, and programming models which are designed for current hardware platforms. Instead, new hardware technologies, coupled with improved programming abstractions and more autonomous runtime systems, are required to achieve this goal. This position paper presents the design of a new runtime for a new heterogeneous hardware platform being developed to explore energy efficient, high performance computing. By combining a number of different technologies, this framework will both simplify the programming of current and future HPC applications, as well as automating the scheduling of data and computation across this new hardware platform. In particular, this work explores the use of FPGAs to achieve both the power and performance goals of exascale, as well as utilising the runtime to automatically effect dynamic configuration and reconfiguration of these platforms. 

Runtime Support for Adaptive Power Capping on Heterogeneous SoCs

Power capping is a fundamental method for reducing the energy consumption of a wide range of modern computing environments, ranging from mobile embedded systems to datacentres. Unfortunately, maximising performance and system efficiency under static power caps remains challenging, while maximising performance under dynamic power caps has been largely unexplored. We present an adaptive power capping method that reduces the power consumption and maximizes the performance of heterogeneous SoCs for mobile and server platforms. Our technique combines power capping with coordinated DVFS, data partitioning and core allocations on a heterogeneous SoC with ARM processors and FPGA resources. We design our framework as a run-time system based on OpenMP and OpenCL to utilise the heterogeneous resources. We evaluate it through five data-parallel benchmarks on the Xilinx SoC which allows fully voltage and frequency control. Our experiments show a significant performance boost of 30% under dynamic power caps with concurrent execution on ARM and FPGA, compared to a naive separate approach.