SURFACE-ENHANCED RAMAN-SCATTERING STUDIES OF METALLOPORPHYRINS ON SILVER SOLS, MELLFS, AND ELECTRODES - EVIDENCE FOR REVERSIBLE PHOTOINDUCED DEMETALATION OF A SILVER(II) PORPHYRIN

A series of metalloporphyrins of the type M(TMPyP) (where M = Ag(II), Zn(II), Cu(II) and TMPyP = meso-tetrakis(4-N-methylpyridyl)porphyrin) have been investigated in solution and on the surface of silver sols, electrodes, and MELLFs (metal liquidlike films). Similar spectra were recorded on all three surfaces but significant differences in detailed behavior were found. In particular, a novel, reversible, and rapid photoinduced demetalation reaction has been observed for the AgII(TMPyP)/MELLF system. An apparently similar demetalation reaction for the same metalloporphyrin was observed on Ag electrodes but this reversed at a very much slower rate. No demetalation of Ag(II)(TMPyP) was observed with Ag sols nor with any of the other metalloporphyrins at any of the surfaces investigated. The implications of the findings in relation to the nature of the MELLF environment are briefly considered.

Development and independent validation of a prognostic assay for stage ii colon cancer using formalin-fixed paraffin-embedded tissue

Purpose: Current prognostic factors are poor at identifying patients at risk of disease recurrence after surgery for stage II colon cancer. Here we describe a DNA microarray-based prognostic assay using clinically relevant formalin-fixed paraffin-embedded (FFPE) samples. Patients and Methods: A gene signature was developed from a balanced set of 73 patients with recurrent disease (high risk) and 142 patients with no recurrence (low risk) within 5 years of surgery. Results: The 634-probe set signature identified high-risk patients with a hazard ratio (HR) of 2.62 (P <.001) during cross validation of the training set. In an independent validation set of 144 samples, the signature identified high-risk patients with an HR of 2.53 (P <.001) for recurrence and an HR of 2.21 (P = .0084) for cancer-related death. Additionally, the signature was shown to perform independently from known prognostic factors (P <.001). Conclusion: This gene signature represents a novel prognostic biomarker for patients with stage II colon cancer that can be applied to FFPE tumor samples. © 2011 by American Society of Clinical Oncology.

Taking pluralism seriously:Embedded moralities in management accounting and control systems

Professor Norman Macintosh has long been a leading, and at times a dissonant, voice in critical accounting studies, exhibiting an intellectual dexterity seldom encountered in the accounting academy. His work ranges from the application of traditional organizational theories within work organizations to poststructural renderings of capital market exigencies. Here, we consider and extend Professor Macintosh's work contemplating the morality embedded within, and propagated by, management accounting and control systems (macs). We begin with Macintosh (1995) employing structuration theory in investigating the ethics of profit manipulation within large, decentralized corporations. The work highlights the fundamental dialectical contradictions within these work organizations, demonstrates the indeterminacy of traditional ethical reasoning, and shows the extent to which macs provide legitimating underpinnings for management action. We propose to extend the conversation using the tools provided in Macintosh's subsequent work: a Levinasian ethic (Macintosh et al., 2009), and heteroglossic accounting (Macintosh, 2002)—both emerging from his poststructuralist predilections. A Levinasian perspective provides an ontologically grounded ethic, and heteroglossic accounting calls for multiple accountings representing alternative moral voices. A critical dialogic framework is proposed as a theoretic for imagining heteroglossic accounting that takes pluralism seriously by recognizing the reality of irresolvable differences and asymmetric power relationships associated with assorted moral perspectives.

Solid-state sodium-selective sensors based on screen-printed Ag/AgCl reference electrodes

The potentiometric and AC impedance characteristics of all solid-state sodium-selective electrodes based on planar screen-printed Ag/AgCl electrodes are described. Two solid-state designs have been investigated. The first was based on the deposition of a sodium-selective PVC membrane directly on top of a screen-printed Ag/AgCl electrode, The second design included a NaCl doped hydrogel layer, between the PVC and Ag\AgCl layers. The hydrogel provides a mechanism to relieve any blockage to charge transfer occurring when PVC membranes are used directly on top of Ag/AgCl and also improves adhesion between the two layers. Results suggest the electrodes display Fast ion exchange kinetics, low noise and drift. The performance compares favorably to that of a conventional ion-selective electrode with internal filling solution.

Interfacial Properties of LiTFSI and LiPF6-Based Electrolytes in Binary and Ternary Mixtures of Alkylcarbonates on Graphite Electrodes and Celgard Separator

For a better understanding of the adsorption behavior of alkylcarbonate-based electrolytes on graphite electrodes and Celgard separator for Li-ion batteries applications, the interface parameters are determined by contact angle and surface tension measurements. The correlation between these parameters and chemical compositions made of alkyl carbonate with a varying nature of lithium salts (LiPF6 and LiTFSI) and volume fractions of binary and ternary mixtures containing propylene carbonate (PC), ethylene carbonate (EC), and dimethyl carbonate (DMC) is investigated. From the obtained contact angle and surface tension (?L) values for each liquid, the dispersive and polar components of the surface tension (?Ld and ?Lp) of the electrolyte and interfacial free energy between the solid and liquid (?SL) were then calculated using the Young’s equation. The variation of contact angle (?) and the surface tension, as well as the work of adhesion (WA) of binary PC/DMC mixtures on PP, PE, and PET model surfaces were also measured and commented as function of volume fraction of PC in DMC. Finally, the Zisman’s critical surface tension (?C) for studied surfaces was then obtained showing positives slopes of cos ? versus ?L. This behavior is explained by a relative higher adsorption of alkylcarbonates to the hydrogenated supports or graphite. These results are decisive to understand the performance of electrolyte/electrode material/separator interfaces in lithium-ion battery devices.

The MNC as an externally embedded organization: An investigation of embeddedness overlap in local subsidiary networks

MNCs have been conceptualized as differentiated networks that, in turn, are embedded in external networks. Previous research has predominantly focused on the embeddedness of established subsidiaries into their local environment, omitting to shed light on the phenomenon of headquarters linkages to the local context which creates embeddedness overlap. We develop a model of why MNCs develop overlapping linkages to local subsidiary networks even if the subsidiaries have grown out of the initial start-up phase. Using detailed information on 168 European subsidiaries, we find that MNCs build and maintain more overlapping network ties when subsidiaries are high performers, hold important resources, operate in turbulent environments, and are closely connected to multinational actors as opposed to purely domestic firms.

Assessing and measuring impact of a digital collection in the humanities: An analysis of the SPHERE (Stormont Parliamentary Hansards: Embedded in Research and Education) Project

Although a substantial corpus of digital materials is now available to scholarship across the disciplines, objective evidence of their use, impact, and value, based on a robust assessment, is sparse. Traditional methods of assessment of impact in the humanities, notably citation in scholarly publications, are not an effective way of assessing impact of digital content. These issues are problematic in the field of Digital Humanities where there is a need to effectively assess impact to justify its continued funding and existence. A number of qualitative and quantitative methods exist that can be used to monitor the use of digital resources in various contexts although they have yet to be applied widely. These have been made available to the creators, managers, and funders of digital content in an accessible form through the TIDSR (Toolkit for the Impact of Digital Scholarly Resources) developed by the Oxford Internet Institute. In 2011, the authors of this article developed the SPHERE project (Stormont Parliamentary Hansards: Embedded in Research and Education) specifically to use TIDSR to evaluate the use and impact of The Stormont Papers, a digital collection of the Hansards of the Stormont Northern Irish Parliament from 1921 to 1972. This article presents the methodology, findings, and analysis of the project. The authors argue that TIDSR is a useful and, critically, transferrable method to understand and increase the impact of digital resources. The findings of the project are modified into a series of wider recommendations on protecting the investment in digital resources by increasing their use, value, and impact. It is reasonable to suggest that effectively showing the impact of Digital Humanities is critical to its survival.

Embedded C programming: a practical course introducing programmable microprocessors

This paper presents a new laboratory-based module for embedded systems teaching, which addresses the current lack of consideration for the link between hardware development, software implementation, course content and student evaluation in a laboratory environment. The course introduces second year undergraduate students to the interface between hardware and software and the programming of embedded devices; in this case, the PIC (originally peripheral interface controller, later rebranded programmable intelligent computer) microcontroller. A hardware development board designed for use in the laboratories of this module is presented. Through hands on laboratory experience, students are encouraged to engage with practical problem-solving exercises and develop programming skills across a broad range of scenarios.

Combined studies of DFT atomistic modelling and in situ FTIR spectroscopy on surface oxidants and CO oxidation at Ru electrodes

We report the combined studies of density functional theory (DFT) calculations and electrochemical in situ FTIR spectroscopy on surface oxidants and mechanisms of CO oxidation at the Ru(0001) electrodes. It is shown that CO can co-adsorb with both O and OH species at lower potential region where a low coverage of the (2 x 2)-O/OH adlayer formed; the oxidation of CO adsorbates takes place at higher potentials where a high coverage of the (1 x 1)-O/OH adlayer formed. Surface O species are not the active oxidants under all coverages studied, due to the high reaction barriers between CO and O (>1 eV). However, surface OH species with higher coverage are identified as the active oxidants, and CO oxidation takes place via a two-steps' mechanism of CO + 3OH -> COOH + 2OH -> CO2 + H2O + OH, in which three nearby OH species are involved in the CO2 formation: CO reacts with OH, forming COOH; COOH then transfers the H to a nearby OH to form H2O and CO2, at the same time, another H in the H2O transfers to a nearby OH to form a weak adsorbed H2O and a new OH. The reaction barrier of these processes is reduced significantly to around 0.50 eV. These new results not only provide an insight into surface active oxidants on Ru, which is directly relevant to fuel cell catalysis, but also reveals the extra complexity of catalytic reactions taking place at solid/liquid electrochemical interface in comparison to the relatively simpler ones at solid/gas phase. 

Developing mRNA-based biomarkers from formalin-fixed paraffin-embedded tissue

Cancer is a complex and heterogeneous disease which is one of the leading causes of death in Western civilisations. Thus, oncology is viewed as a primary focus for personalized medicine. It is recognised that cancer treatment needs to be better tailored in order to improve patient outcome. Patient tumor samples will be required to characterize cancer at a molecular level and identify where there may be disease subgroups that should be treated differently. The use of formalin-fixed paraffin-embedded tissue is important for enabling such studies. In this report, we focus on the challenges that have been faced to date along with the technological developments that have now made this possible. We also highlight the impact this may have on drug and diagnostic development.

SPHERE: Stormont Parliamentary Hansards: Embedded in Research and Education

SPHERE (Stormont Parliamentary Hansards: Embedded in Research and Education) was a JISC-funded project based at King’s College, London and Queen’s University, Belfast, working in Partnership with the Northern Ireland Assembly Library, and the NIA Official Report (Hansard). Its purpose was to assess the use, value and impact of The Stormont Papers digital resource, and to use the results of this assessment to make recommendations for a series of practical approaches to embed the resource within teaching, learning and research among the wider user community. The project began in November 2010 and was concluded in April 2010.

A series of formal reports on the project are published by JISC online at http://www.jisc.ac.uk/whatwedo/programmes/digitisation/impactembedding/sphere.aspx

SPHERE Impact analysis summary
Portable Document Format
SPHERE interviews report
SPHERE Outreach use case
SPHERE research use case
SPHERE teaching use_case
SPHERE web survey report
SPHERE web analysis

Rational screening low-cost counter electrodes for dye-sensitized solar cells

Dye-sensitized solar cells have attracted intense research attention owing to their ease of fabrication, cost-effectiveness and high efficiency in converting solar energy. Noble platinum is generally used as catalytic counter electrode for redox mediators in electrolyte solution. Unfortunately, platinum is expensive and non-sustainable for long-term applications. Therefore, researchers are facing with the challenge of developing low-cost and earth-abundant alternatives. So far, rational screening of non-platinum counter electrodes has been hamstrung by the lack of understanding about the electrocatalytic process of redox mediators on various counter electrodes. Here, using first-principle quantum chemical calculations, we studied the electrocatalytic process of redox mediators and predicted electrocatalytic activity of potential semiconductor counter electrodes. On the basis of theoretical predictions, we successfully used rust (alpha-Fe2O3) as a new counter electrode catalyst, which demonstrates promising electrocatalytic activity towards triiodide reduction at a rate comparable to platinum.

Electrocatalytic activity of Ru-modified Pt(111) electrodes toward CO oxidation

The electrochemical deposition of Ru on Pt(111) electrodes has been investigated by electron diffraction, Auger spectroscopy, and cyclic voltammetry in a closed UHV transfer system. At small coverages Ru formed a monatomic commensurate layer, at higher coverage mostly small islands with a bilayer height were detected. When the Pt was almost completely covered by Ru, three-dimensional clusters developed. The island structure of Ru changed upon electrooxidation of CO, reflecting an enhanced mobility of Ru. Adsorption and electrooxidation of CO have been studied on such Ru-modified Pt(111) electrodes using cyclic voltammetry and in situ FTIR spectroscopy. Compared to the pure metals, the Ru-CO bond is weakened, the Pt-CO bond strengthened on the modified electrodes. The catalytic activity of the Ru/Pt(111) electrode toward CO adlayer oxidation is higher than that of pure Ru and a PtRu alloy (50:50). It is concluded that the electrooxidation of CO takes place preferentially at the Ru islands, while CO adsorbed on Pt migrates to them. © 1999 American Chemical Society.