Multistep electrochemical reduction path of clusters [Os3(CO)10(α-diimine)]: comparison of electrochemical and photochemical Os-Os(α-diimine) bond cleavage

Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ability of the reducible alpha-dimine ligand, which decreases in the order mu-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(alpha-dimine) chelate ring causes weakening of the axial (CO)(4)Os-Os(CO)(2)(alpha-dimine) bond and its facile cleavage for alpha-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest pi-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re( bpym) chelate bond, the Os-3-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os-3(CO)(10)(bpym)](center dot-) at T = 223 K gives the open-triosmium core (= Os-3*) dianion, [Os-3*(CO)(10)(bpym)](2-). Its oxidation leads to the recovery of parent [Os-3(CO)(10)( bpym)]. At room temperature, [Os-3*( CO)(10)(bpym)](2-) is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open- core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os-3*(CO)(10)( bpym)](2-) rapidly attacks yet non- reduced parent cluster molecules, producing the relatively stable open- core dimer [Os-3*(CO)(10)(bpym)](2)(2-) featuring two open- triangle cluster moieties connected with an ( bpym) Os - Os( bpym) bond. In butyronitrile, [Os-3*( CO)(10)(bpym)](2-) is stabilised by the solvent and the dimer [Os-3*(CO)(10)(bpym)](2)(2-) is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os-3(CO)(10)(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os-3*(CO)(10)(alpha- diimine)](2)(2-). The products formed are [Os-2(CO)(8)](2-) and {Os(CO)(2)(alpha- diimine)}(2). The latter dinuclear fragments constitute a linear polymeric chain [Os( CO)(2)(alpha-dimine)] n that is further reducible at the alpha-dimine ligands. For alpha-dimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os-3( CO)(10)(alpha-dimine)] clusters exhibits several common features with their photochemistry. The same Os-alpha-dimine bond dissociates in both cases but the intimate mechanisms are different.

Purification and functional characterisation of Rhinocerase, a novel serine protease from the venom of Bitis gabonica rhinoceros

Background: Serine proteases are a major component of viper venoms and are thought to disrupt several distinct elements of the blood coagulation system of envenomed victims. A detailed understanding of the functions of these enzymes is important both for acquiring a fuller understanding of the pathology of envenoming and because these venom proteins have shown potential in treating blood coagulation disorders. Methodology/Principal Findings: In this study a novel, highly abundant serine protease, which we have named rhinocerase, has been isolated and characterised from the venom of Bitis gabonica rhinoceros using liquid phase isoelectric focusing and gel filtration. Like many viper venom serine proteases, this enzyme is glycosylated; the estimated molecular mass of the native enzyme is approximately 36kDa, which reduces to 31kDa after deglycosylation. The partial amino acid sequence shows similarity to other viper venom serine proteases, but is clearly distinct from the sequence of the only other sequenced serine protease from Bitis gabonica. Other viper venom serine proteases have been shown to exert distinct biological effects, and our preliminary functional characterization of rhinocerase suggest it to be multifunctional. It is capable of degrading α and β chains of fibrinogen, dissolving plasma clots and of hydrolysing a kallikrein substrate. Conclusions/Significance: A novel multifunctional viper venom serine protease has been isolated and characterised. The activities of the enzyme are consistent with the known in vivo effects of Bitis gabonica envenoming, including bleeding disorders, clotting disorders and hypotension. This study will form the basis for future research to understand the mechanisms of serine protease action, and examine the potential for rhinocerase to be used clinically to reduce the risk of human haemostatic disorders such as heart attacks and strokes.

Should we be utopophobes about democracy in particular?

In his book Democratic Authority, David Estlund puts forward a case for democracy, which he labels epistemic proceduralism, that relies on democracy's ability to produce good – that is, substantively just – results. Alongside this case for democracy Estlund attacks what he labels ‘utopophobia’, an aversion to idealistic political theory. In this article I make two points. The first is a general point about what the correct level of ‘idealisation’ is in political theory. Various debates are emerging on this question and, to the extent that they are focused on ‘political theory’ as a whole, I argue, they are flawed. This is because there are different kinds of political concept, and they require different kinds of ideal. My second point is about democracy in particular. If we understand democracy as Estlund does, then we should see it as a problem-solving concept – the problem being that we need coercive institutions and rules, but we do not know what justice requires. As democracy is a response to a problem, we should not allow our theories of it, even at the ideal level, to be too idealised – they must be embedded in the nature of the problem they are to solve, and the beings that have it.

Virtual reality Post Traumatic Stress Disorder (PTSD) exposure therapy results with active duty OIF/OEF service members

Posttraumatic stress disorder (PTSD) is reported to be caused by exposure to traumatic events including (but not limited to) military combat, violent personal assault, being kidnapped or taken hostage and terrorist attacks. Initial data suggest that at least 1 out of 6 Iraq War veterans are exhibiting symptoms of depression, anxiety and PTSD. Virtual reality (VR) delivered exposure therapy for PTSD has been used with reports of positive outcomes. The aim of the current paper, is to present the rationale and brief description of a Virtual Iraq/Afghanistan PTSD VR therapy application and present initial findings from its use with PTSD patients. Thus far, Virtual Iraq/Afghanistan consists of a series of customizable virtual scenarios designed to represent relevant Middle Eastern VR contexts for exposure therapy, including a city and desert road convoy environment. User-centered design feedback, needed to iteratively evolve the system, was gathered from returning Iraq War veterans in the USA and from a system deployed in Iraq and tested by an Army Combat Stress Control Team. Results from an open clinical trial at San Diego Naval Medical Center of the first 20 treatment completers indicate that 16 no longer met PTSD screening criteria at post-treatment, with only one not maintaining treatment gains at 3 month follow-up.

Spatial patterns of office employment in the New York region

This study analyzes the regional spatial dynamics of the New York region for a period of roughly twenty years and places the effects of the 9/11 terrorist attacks in the context of longer-term regional dynamics. The analysis reveals that office-using industries are still heavily concentrated in Manhattan despite ongoing decentralization in many of these industries over the last twenty years. Financial services tend to be highly concentrated in Manhattan whereas administrative and support services are the least concentrated of the six major office-using industry groups. Although office employment has been by and large stagnant in Manhattan for at least two decades, growth of output per worker has outpaced the CMSA as well as the national average. This productivity differential is mainly attributable to competitive advantages of office-using industries in Manhattan and not to differences in industry composition. Finally, the zip-code level analysis of the Manhattan core area yielded further evidence of the existence of significant spillover effects at the small-scale level.

How many Frenchmen did you kill? British bombing policy towards France (1940-1945)

The Allied bombing of France between 1940 and 1945 has received comparatively little attention from historians, although the civilian death toll, at about 60,000, was comparable to that of German raids on the UK. This article considers how Allied, and particularly British, bombing policy towards France was developed, what its objectives were and how French concerns about attacks on their territory were (or were not) addressed. It argues that while British policymakers were sensitive to the delicate political implications of attacking France, perceived military necessities tended to trump political misgivings; that Vichy, before November 1942, was a stronger constraint on Allied bombing than the Free French at any time and that the bombing programme largely escaped political control from May 1944.

A national security strategy for England: Matthew Sutcliffe, the Earl of Essex, and the Cadiz Expedition of 1596

The English cleric Matthew Sutcliffe arguably produced the first comprehensive security concept in history. It had at its centre the war between England and Spain (1585-1604), and Sutcliffe advocated taking the war to the Iberian Peninsula to seize Philip II's main Atlantic ports, rather than remaining satisfied with the indirect combat of Spain in Flanders, defensive action against naval attacks on England and the guerre de course on Spanish shipping at sea. This approach seems to be at the heart of Essex's 1596 naval campaing against Spanish ports, which foundered on the bureaucratic politics of the Elizabethan government.

Does terrorism threaten human rights? Evidence from panel data

Using panel data for 111 countries over the period 1982–2002, we employ two indexes that cover a wide range of human rights to empirically analyze whether and to what extent terrorism affects human rights. According to our results,terrorism significantly, but not dramatically, diminishes governments’ respect for basic human rights such as the absence of extrajudicial killings, political imprisonment, and torture. The result is robust to how we measure terrorist attacks, to the method of estimation, and to the choice of countries in our sample. However, we find no effect of terrorism on empowerment rights.

Terrorist transgressions: gendered representations of the terrorist in visual culture

The aim of Terrorist Transgressions is to analyse the myths inscribed in images of the terrorist and identify how agency is attributed to representation through invocations and inversions of gender stereotypes. In modern discourses on the terrorist the horror experienced in Western societies was the appearance of a new sense of the vulnerability of the body politic, and therefore of the modern self with its direct dependency on security and property. The terrorist has been constructed as the epitome of transgression against economic resources and moral, physical and political boundaries. Although terrorism has been the focus of intense academic activity, cultural representations of the terrorist have received less attention. Yet terrorism is dependent on spectacle and the topic is subject to forceful exposure in popular media. While the terrorist is predominantly aligned with masculinity, women have been active in terrorist organisations since the late 19th century and in suicidal terrorist attacks since the 1980s. Such attacks have confounded constructions of femininity and masculinity, with profound implications for the gendering of violence and horror. The publication arises from an AHRC networking grant, 2011-12, with Birkbeck, and includes collaboration with the army at Sandhurst RMA. The project relates to a wider investigation into feminism, violence and contemporary art.

International terrorism, domestic political instability, and the escalation effect

What are the main causes of international terrorism? Despite the meticulous examination of various candidate explanations, existing estimates still diverge in sign, size, and significance. This article puts forward a novel explanation and supporting evidence. We argue that domestic political instability provides the learning environment needed to successfully execute international terror attacks. Using a yearly panel of 123 countries over 1973–2003, we find that the occurrence of civil wars increases fatalities and the number of international terrorist acts by 45%. These results hold for alternative indicators of political instability, estimators, subsamples, subperiods, and accounting for competing explanations.

Lock, stock, and barrel: a comprehensive assessment of the determinants of terror

We assess the robustness of previous findings on the determinants of terrorism. Using extreme bound analysis, the three most comprehensive terrorism datasets, and focusing on the three most commonly analyzed aspects of terrorist activity, i.e., location, victim, and perpetrator, we re-assess the effect of 65 proposed correlates. Evaluating around 13.4 million regressions, we find 18 variables to be robustly associated with the number of incidents occurring in a given country-year, 15 variables with attacks against citizens from a particular country in a given year, and six variables with attacks perpetrated by citizens of a particular country in a given year.

Does political proximity to the U.S. cause terror?

We analyze the impact of political proximity to the United States on the occurrence and severity of terror. Employing panel data for 116 countries over the period 1975–2001 we find that countries voting in line with the U.S. are victims of more and deadlier attacks.

Attacking human implants: a new generation of cybercrime

Human ICT implants, such as RFID implants, cochlear implants, cardiac pacemakers, Deep Brain Stimulation, bionic limbs connected to the nervous system, and networked cognitive prostheses, are becoming increasingly complex. With ever-growing data processing functionalities in these implants, privacy and security become vital concerns. Electronic attacks on human ICT implants can cause significant harm, both to implant subjects and to their environment. This paper explores the vulnerabilities which human implants pose to crime victimisation in light of recent technological developments, and analyses how the law can deal with emerging challenges of what may well become the next generation of cybercrime: attacks targeted at technology implanted in the human body. After a state-of-the-art description of relevant types of human implants and a discussion how these implants challenge existing perceptions of the human body, we describe how various modes of attacks, such as sniffing, hacking, data interference, and denial of service, can be committed against implants. Subsequently, we analyse how these attacks can be assessed under current substantive and procedural criminal law, drawing on examples from UK and Dutch law. The possibilities and limitations of cybercrime provisions (eg, unlawful access, system interference) and bodily integrity provisions (eg, battery, assault, causing bodily harm) to deal with human-implant attacks are analysed. Based on this assessment, the paper concludes that attacks on human implants are not only a new generation in the evolution of cybercrime, but also raise fundamental questions on how criminal law conceives of attacks. Traditional distinctions between physical and non-physical modes of attack, between human bodies and things, between exterior and interior of the body need to be re-interpreted in light of developments in human implants. As the human body and technology become increasingly intertwined, cybercrime legislation and body-integrity crime legislation will also become intertwined, posing a new puzzle that legislators and practitioners will sooner or later have to solve.

Biometrics in ABC: counter-spoofing research

Automated border control (ABC) is concerned with fast and secure processing for intelligence-led identification. The FastPass project aims to build a harmonised, modular reference system for future European ABC. When biometrics is taken on board as identity, spoofing attacks become a concern. This paper presents current research in algorithm development for counter-spoofing attacks in biometrics. Focussing on three biometric traits, face, fingerprint, and iris, it examines possible types of spoofing attacks, and reviews existing algorithms reported in relevant academic papers in the area of countering measures to biometric spoofing attacks. It indicates that the new developing trend is fusion of multiple biometrics against spoofing attacks.

Enhanced three-factor security protocol for consumer USB mass storage devices

The Universal Serial Bus (USB) is an extremely popular interface standard for computer peripheral connections and is widely used in consumer Mass Storage Devices (MSDs). While current consumer USB MSDs provide relatively high transmission speed and are convenient to carry, the use of USB MSDs has been prohibited in many commercial and everyday environments primarily due to security concerns. Security protocols have been previously proposed and a recent approach for the USB MSDs is to utilize multi-factor authentication. This paper proposes significant enhancements to the three-factor control protocol that now makes it secure under many types of attacks including the password guessing attack, the denial-of-service attack, and the replay attack. The proposed solution is presented with a rigorous security analysis and practical computational cost analysis to demonstrate the usefulness of this new security protocol for consumer USB MSDs.