Using matrix peaks to map topography: increased mass resolution and enhanced sensitivity in chemical imaging

It is well known in secondary ion mass spectrometry (SIMS) that sample topography leads to decreased mass resolution. Specifically, the ion's time of flight is dependent on where it was generated. Here, using matrix-enhanced SIMS, it is demonstrated that, in addition to increasing the yield of intact pseudomolecular ions, the matrix allows the user to semiquantitatively record the topography of a sample. Through mapping the topography-related mass shifts of the matrix (which leads to decreased mass resolution), the analogous mass shifts of higher mass ions can be deconvoluted and higher resolution and greater sensitivity obtained. Furthermore, the semiquantitative topographical map obtained can be compared with any chemical images obtained, allowing the user to quickly ascertain whether local intensity maximums are due to topological features or represent genuine features of interest.     

A logistic regression framework for information technology outsourcing lifecycle management

We present a methodology for managing outsourcing projects from the vendor's perspective, designed to maximize the value to both the vendor and its clients. The methodology is applicable across the outsourcing lifecycle, providing the capability to select and target new clients, manage the existing client portfolio and quantify the realized benefits to the client resulting from the outsourcing agreement. Specifically, we develop a statistical analysis framework to model client behavior at each stage of the outsourcing lifecycle, including: (1) a predictive model and tool for white space client targeting and selection—opportunity identification (2) a model and tool for client risk assessment and project portfolio management—client tracking, and (3) a systematic analysis of outsourcing results, impact analysis, to gain insights into potential benefits of IT outsourcing as a part of a successful management strategy. Our analysis is formulated in a logistic regression framework, modified to allow for non-linear input–output relationships, auxiliary variables, and small sample sizes. We provide examples to illustrate how the methodology has been successfully implemented for targeting, tracking, and assessing outsourcing clients within IBM global services division.Scope and purposeThe predominant literature on IT outsourcing often examines various aspects of vendor–client relationship, strategies for successful outsourcing from the client perspective, and key sources of risk to the client, generally ignoring the risk to the vendor. However, in the rapidly changing market, a significant share of risks and responsibilities falls on vendor, as outsourcing contracts are often renegotiated, providers replaced, or services brought back in house. With the transformation of outsourcing engagements, the risk on the vendor's side has increased substantially, driving the vendor's financial and business performance and eventually impacting the value delivery to the client. As a result, only well-ran vendor firms with robust processes and tools that allow identification and active management of risk at all stages of the outsourcing lifecycle are able to deliver value to the client. This paper presents a framework and methodology for managing a portfolio of outsourcing projects from the vendor's perspective, throughout the entire outsourcing lifecycle. We address three key stages of the outsourcing process: (1) opportunity identification and qualification (i.e. selection of the most likely new clients), (2) client portfolio risk management during engagement and delivery, and (3) quantification of benefits to the client throughout the life of the deal.     

Clearing the mind: A working memory model of distraction from negative mood.

The present research examined whether and how loading working memory can attenuate negative mood. In three experiments, participants were exposed to neutral, weakly negative, or strongly negative pictures followed by a task and a mood scale. Working memory demands were varied by manipulating task presence (Study 1), complexity (Study 2), and predictability (Study 3). Participants in all three experiments reported less negative moods in negative trials with high compared to low working memory demand. Working memory demands did not affect mood in the neutral trials. When working memory demands were high, participants no longer reported more negative moods in response to strongly negative pictures than to weakly negative pictures. These findings suggest that loading working memory prevents mood-congruent processing, and thereby promotes distraction from negative moods. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The Periplasmic Oxidoreductase DsbA Is Required for Virulence of the Phytopathogen Dickeya solani

In bacteria, the DsbA oxidoreductase is a crucial factor responsible for the introduction of disulfide bonds to extracytoplasmic proteins, which include important virulence factors. A lack of proper disulfide bonds frequently leads to instability and/or loss of protein function; therefore, improper disulfide bonding may lead to avirulent phenotypes. The importance of the DsbA function in phytopathogens has not been extensively studied yet. Dickeya solani is a bacterium from the Soft Rot Pectobacteriaceae family which is responsible for very high economic losses mainly in potato. In this work, we constructed a D. solani dsbA mutant and demonstrated that a lack of DsbA caused a loss of virulence. The mutant bacteria showed lower activities of secreted virulence determinants and were unable to develop disease symptoms in a potato plant. The SWATH-MS-based proteomic analysis revealed that the dsbA mutation led to multifaceted effects in the D. solani cells, including not only lower levels of secreted virulence factors, but also the induction of stress responses. Finally, the outer membrane barrier seemed to be disturbed by the mutation. Our results clearly demonstrate that the function played by the DsbA oxidoreductase is crucial for D. solani virulence, and a lack of DsbA significantly disturbs cellular physiology.     

Studies of the Influence of Temperature and the Energy State of the Surface Layer of Adsorbents on Wall Effects in Soap-Based Greases

This paper presents the results of studies of wall effects in commercial soap-based greases LT4-S2 and HUTPLEX EP-2, thickened with, respectively, lithium 12-hydroxystearate and overbased calcium sulfonate. The studies were conducted in the presence of five different materials: copper alloy C11000, bronze B476, EPDM rubber and PTFE and PU thermoplastics. The influence of the energy state of the surface layer of the adsorbents and temperature (ranging from ?20 to 60 °C) on the intensity of wall effects was investigated. Changes in the structural viscosity and shear stress in the boundary layer area in the greases and the soap-based thickener’s ability to adsorb on the surfaces of the adsorbents were determined by evaluating the rheological parameter plateau modulus.     

Verification of cardiac tissue electrophysiology simulators using an N-version benchmark

Ongoing developments in cardiac modelling have resulted, in particular, in the development of advanced and increasingly complex computational frameworks for simulating cardiac tissue electrophysiology. The goal of these simulations is often to represent the detailed physiology and pathologies of the heart using codes that exploit the computational potential of high-performance computing architectures. These developments have rapidly progressed the simulation capacity of cardiac virtual physiological human style models; however, they have also made it increasingly challenging to verify that a given code provides a faithful representation of the purported governing equations and corresponding solution techniques. This study provides the first cardiac tissue electrophysiology simulation benchmark to allow these codes to be verified. The benchmark was successfully evaluated on 11 simulation platforms to generate a consensus gold-standard converged solution. The benchmark definition in combination with the gold-standard solution can now be used to verify new simulation codes and numerical methods in the future.     

On the evaluation of unsupervised outlier detection: measures,datasets, and an empirical study

The evaluation of unsupervised outlier detection algorithms is a constant challenge in data mining research. Little is known regarding the strengths and weaknesses of different standard outlier detection models, and the impact of parameter choices for these algorithms. The scarcity of appropriate benchmark datasets with ground truth annotation is a significant impediment to the evaluation of outlier methods. Even when labeled datasets are available, their suitability for the outlier detection task is typically unknown. Furthermore, the biases of commonly-used evaluation measures are not fully understood. It is thus difficult to ascertain the extent to which newly-proposed outlier detection methods improve over established methods. In this paper, we perform an extensive experimental study on the performance of a representative set of standard k nearest neighborhood-based methods for unsupervised outlier detection, across a wide variety of datasets prepared for this purpose. Based on the overall performance of the outlier detection methods, we provide a characterization of the datasets themselves, and discuss their suitability as outlier detection benchmark sets. We also examine the most commonly-used measures for comparing the performance of different methods, and suggest adaptations that are more suitable for the evaluation of outlier detection results.     

Effect of Oligothienyl Chain Length on Tuning the Solar Cell Performance in Fluorene‐Based Polyplatinynes

A series of solution‐processable and strongly visible‐light absorbing polyplatinynes containing oligothienyl–fluorene ring hybrids were synthesized and characterized. These rigid‐rod organometallic materials are soluble in polar organic solvents and show intense absorptions in the visible spectral region, rendering them excellent candidates for bulk heterojunction polymer solar cells. The photovoltaic behavior depends significantly on the number of thienyl rings along the polymer chain, and some of these polymer solar cells show high power conversion efficiencies (PCEs) of up to 2.9% and a peak external quantum efficiency to 83% under AM1.5 simulated solar illumination. The effect of oligothienyl chain length on improving the polymer solar cell efficiency and on their optical and charge transport properties is elucidated in detail. At the same blend ratio of 1:5, the light‐harvesting capability and PCE increase markedly with increasing number of thienyl rings. The power dependencies of the solar cell parameters (including the short‐circuit current density, open‐circuit voltage, fill‐factor, and PCE) were also examined. The present work opens up an attractive avenue to developing conjugated metallopolymers with broad and strong solar energy absorptions and tunable solar cell efficiency and supports the potential of metalated conjugated polymers for efficient power generation.     

The role of MCM-41 composition in the creation of basicity by alkali metal impregnation

Three types of mesoporous molecular sieves (silicate MCM-41, niobosilicate NbMCM-41, and aluminosilicate AlMCM-41) were impregnated with alkali metal acetates. The textural stability of the samples was estimated on the basis of XRD measurements and nitrogen adsorption/desorption methods. The acidic–basic properties of the obtained materials were tested in the cyclization of acetonylacetone and studied by FTIR spectroscopy after adsorption of methylacetylene (propyne) and pyridine. Two types of chemical reactions between mesoporous matrix and alkali metal salt/oxide were observed: the reaction between alkali metal salt and silica/silicate and the reaction between basic oxide and silanol groups or Na⁺ cations. In the first one the alkali metal silicate formation decreases from Li to Cs species and leads to the destruction of the material. The second reaction places alkali metal cations in extra framework positions, which increases from Li to Cs species and is only observed in the case of AlMCM-41 and NbMCM-41 materials. As a result of the second reaction Lewis acidity is generated. The average effect of these two interactions leads to the volcanic curve for basicity of M/AlMCM-41 and M/NbMCM-41 with the maximum for K-samples. In contrast, basicity of M/MCM-41 systematically increases from Li to Cs form since the second type of interaction does not occur for these samples.