Structural studies of trans-N2S2 copper macrocycles

The X-ray crystal structures of two related trans-N2S2 copper macrocycles are reported. One was isolated with the copper in the divalent form and the other with copper in its univalent form affording a valuable insight into the changes of geometry and metrical parameters that occur during redox processes in macrocyclic copper complexes. A variable temperature NMR study of the copper(I) complex is reported, indicative of a chair-boat conformational change within the alkyl chain backbone of the macrocycle. It was possible to extract the relevant kinetic and thermodynamic parameters (?G‡, 57.8 kJ mol-1; ?H‡, 52.1 kJ mol-1; ?S‡, -19.2 J K-1 mol-1) for this process at 298 K. DFT molecular orbital calculations were used to confirm these observations and to calculate the energy difference (26.2 kJmol-1) between the copper(I) macrocycle in a planar and a distorted tetrahedral disposition.

Behind the scenes:a week in the life of a Senior Pro-Vice Chancellor

Helen Higson graduated from Cambridge University in 1982 and followed this up with an MSc with the Open University and a PhD at Birkbeck College London. She started working in HE at Southampton University and has spent the last 25 years at Aston University. Her roles there have been various, starting as PA to the Pro-Vice-Chancellor External Relations and spending 20 years with Aston Business School. Helen was awarded a Personal Chair in Higher Education Learning and Management in 2008 and is currently Senior Pro-Vice-Chancellor, with responsibility for International Relations, Employability, Schools Liaison, Registry and Planning. Helen was awarded an AUA Fellowship in 2010 and an OBE in the 2011 New Year Honours list.

Giving whistleblowers greater protection:improving quality of care

This year, an independent review of whisleblowing in the NHS made recommendations as to how whistleblowers could be given greater protection. The review, chaired by Sir Robert Francis, intended to improve the quality of patient care and safety in the health service. But with many practitioners remaining unregulated, there are unanswered questions as to how reports of mistakes can be properly investigated and the necessary action taken against incompetent or negligent practitioners. Amanda Casey, Chair of the Registration Council for Clinical Physiologists, makes the case for regulation of professionals whose work poses potential risks to patients and can place healthcare managers in an invidious position.

Preface

The Semantic Web has come a long way since its inception in 2001, especially in terms of technical development and research progress. However, adoption by non- technical practitioners is still an ongoing process, and in some areas this process is just now starting. Emergency response is an area where reliability and timeliness of information and technologies is of essence. Therefore it is quite natural that more widespread adoption in this area has not been seen until now, when Semantic Web technologies are mature enough to support the high requirements of the application area. Nevertheless, to leverage the full potential of Semantic Web research results for this application area, there is need for an arena where practitioners and researchers can meet and exchange ideas and results. Our intention is for this workshop, and hopefully coming workshops in the same series, to be such an arena for discussion. The Extended Semantic Web Conference (ESWC - formerly the European Semantic Web conference) is one of the major research conferences in the Semantic Web field, whereas this is a suitable location for this workshop in order to discuss the application of Semantic Web technology to our specific area of applications. Hence, we chose to arrange our first SMILE workshop at ESWC 2013. However, this workshop does not focus solely on semantic technologies for emergency response, but rather Semantic Web technologies in combination with technologies and principles for what is sometimes called the "social web". Social media has already been used successfully in many cases, as a tool for supporting emergency response. The aim of this workshop is therefore to take this to the next level and answer questions like: "how can we make sense of, and furthermore make use of, all the data that is produced by different kinds of social media platforms in an emergency situation?" For the first edition of this workshop the chairs collected the following main topics of interest: • Semantic Annotation for understanding the content and context of social media streams. • Integration of Social Media with Linked Data. • Interactive Interfaces and visual analytics methodologies for managing multiple large-scale, dynamic, evolving datasets. • Stream reasoning and event detection. • Social Data Mining. • Collaborative tools and services for Citizens, Organisations, Communities. • Privacy, ethics, trustworthiness and legal issues in the Social Semantic Web. • Use case analysis, with specific interest for use cases that involve the application of Social Media and Linked Data methodologies in real-life scenarios. All of these, applied in the context of: • Crisis and Disaster Management • Emergency Response • Security and Citizen Journalism The workshop received 6 high-quality paper submissions and based on a thorough review process, thanks to our program committee, the decision was made to accept four of these papers for the workshop (67% acceptance rate). These four papers can be found later in this proceedings volume. Three out of four of these papers particularly discuss the integration and analysis of social media data, using Semantic Web technologies, e.g. for detecting complex events in social media streams, for visualizing and analysing sentiments with respect to certain topics in social media, or for detecting small-scale incidents entirely through the use of social media information. Finally, the fourth paper presents an architecture for using Semantic Web technologies in resource management during a disaster. Additionally, the workshop featured an invited keynote speech by Dr. Tomi Kauppinen from Aalto university. Dr. Kauppinen shared experiences from his work on applying Semantic Web technologies to application fields such as geoinformatics and scientific research, i.e. so-called Linked Science, but also recent ideas and applications in the emergency response field. His input was also highly valuable for the roadmapping discussion, which was held at the end of the workshop. A separate summary of the roadmapping session can be found at the end of these proceedings. Finally, we would like to thank our invited speaker Dr. Tomi Kauppinen, all our program committee members, as well as the workshop chair of ESWC2013, Johanna Völker (University of Mannheim), for helping us to make this first SMILE workshop a highly interesting and successful event!

Conformational analysis of the natural iron chelator myo-inositol 1,2,3-trisphosphate using a pyrene-based fluorescent mimic

myo-Inositol phosphates possessing the 1,2,3-trisphosphate motif share the remarkable ability to completely inhibit iron-catalysed hydroxyl radical formation. The simplest derivative, myo-inositol 1,2,3-trisphosphate [Ins(1,2,3)P3], has been proposed as an intracellular iron chelator involved in iron transport. The binding conformation of Ins(1,2,3)P3 is considered to be important to complex Fe3+ in a 'safe' manner. Here, a pyrene-based fluorescent probe, 4,6-bispyrenoyl-myo-inositol 1,2,3,5-tetrakisphosphate [4,6-bispyrenoyl Ins(1,2,3,5)P4], has been synthesised and used to monitor the conformation of the 1,2,3-trisphosphate motif using excimer fluorescence emission. Ring-flip of the cyclohexane chair to the penta-axial conformation occurs upon association with Fe3+, evident from excimer fluorescence induced by π-π stacking of the pyrene reporter groups, accompanied by excimer formation by excitation at 351 nm. This effect is unique amongst biologically relevant metal cations, except for Ca 2+ cations exceeding a 1:1 molar ratio. In addition, the thermodynamic constants for the interaction of the fluorescent probe with Fe3+ have been determined. The complexes formed between Fe 3+ and 4,6-bispyrenoyl Ins(1,2,3,5)P4 display similar stability to those formed with Ins(1,2,3)P3, indicating that the fluorescent probe acts as a good model for the 1,2,3-trisphosphate motif. This is further supported by the antioxidant properties of 4,6-bispyrenoyl Ins(1,2,3,5)P4, which closely resemble those obtained for Ins(1,2,3)P3. The data presented confirms that Fe3+ binds tightly to the unstable penta-axial conformation of myo-inositol phosphates possessing the 1,2,3-trisphosphate motif. © 2010 The Royal Society of Chemistry.