Electronic properties of 4,4 ',5,5 '-tetramethyl-2,2 '-biphosphinine (tmbp) in the redox series fac-[Mn(Br)(CO)(3)(tmbp)], [Mn(CO)(3)(tmbp)](2), and [Mn(CO)(3)(tmbp)](-): crystallographic, spectroelectrochemical, and DFT computational study

Stepwise electrochemical reduction of the complex fac-[Mn(Br)(CO)(3)(tmbp)] (tmbp = 4,4',5,5'-tetramethyl-2,2'-biphosphinine) produces the dimer [Mn(CO)(3)(tmbp)](2) and the five-coordinate anion [Mn(CO)(3)(tmbp)](-). All three members of the redox series have been characterized by single-crystal X-ray diffraction. The crystallographic data provide valuable insight into the localization of the added electrons on the (carbonyl)manganese and tmbp centers. In particular, the formulation of the two-electron-reduced anion as [Mn-0(CO)(3)(tmbp(-))](-) also agrees with the analysis of its IR nu(CO) wavenumbers and with the results of density functional theoretical (DFT) MO calculations on this compound. The strongly delocalized pi-bonding in the anion stabilizes its five-coordinate geometry and results in the appearance of several mixed Mn-to-tmbp charge-transfer/IL(tmbp) transitions in the near-UV-vis spectral region. A thorough voltammetric and UV-vis/IR spectroelectrochemical study of the reduction path provided evidence for a direct formation of [Mn(CO)(3)(tmbp)](-) via a two-electron ECE mechanism involving the [Mn(CO)(3)(tmbp)](.) radical transient. At ambient temperature [Mn(CO)(3)(tmbp)](-) reacts rapidly with nonreduced fac-[Mn(Br)(CO)(3)(tmbp)] to produce [Mn(CO)(3)(tmbp)](2). Comparison with the analogous 2,2'-bipyridine complexes has revealed striking similarity in the bonding properties and reactivity, despite the stronger pi-acceptor character of the tmbp ligand.

Video activity extraction and reporting with incremental unsupervised learning

The present work presents a new method for activity extraction and reporting from video based on the aggregation of fuzzy relations. Trajectory clustering is first employed mainly to discover the points of entry and exit of mobiles appearing in the scene. In a second step, proximity relations between resulting clusters of detected mobiles and contextual elements from the scene are modeled employing fuzzy relations. These can then be aggregated employing typical soft-computing algebra. A clustering algorithm based on the transitive closure calculation of the fuzzy relations allows building the structure of the scene and characterises the ongoing different activities of the scene. Discovered activity zones can be reported as activity maps with different granularities thanks to the analysis of the transitive closure matrix. Taking advantage of the soft relation properties, activity zones and related activities can be labeled in a more human-like language. We present results obtained on real videos corresponding to apron monitoring in the Toulouse airport in France.

The strategy makers: thoughts on war and society from Machiavelli and Clausewitz

Introductory chapter. Introduction and excerpts from works of Seigneur de Fourquevaux (1548); Francois Loque – Saillans (1589); Matthew Sutcliffe (1593); Don Bernardino de Mendoza (1595); Paul Hay du Chastelet (1668); Marquis Santa Cruz de Marcenado & Zanthier (1724-30/1775); Guibert (1772); Rühle von Lilienstern (1816/1817).

Sleepwalking from New York to Miami

In the winter of 2007, Doug Aitken’s moving image installation, sleepwalkers, was projected onto the exterior walls of the Museum of Modern Art in New York. The project was a collaboration between Aitken, the museum and Creative Time, a New York-based organisation that commissions public art projects. A site-specific version of the installation has been commissioned by the Miami Art Museum for the opening of its new facility, designed by Swiss architects Herzog and de Meuron, in 2013: “sleepwalkers (Miami) will expand the work’s landscape and characters in a manner that reflects the diverse social fabric of Miami.” This essay examines sleepwalkers as an example of the emerging form of film as public art. There are three strands to my argument: first, an examination of the role of film in the redefinition of public art, shifting away from spatial practices concerned with fixed and permanent notions of space, community and art and towards transient and experimental spatial and artistic practices; second,a discussion of the relationship between projection and the built environment and the ways that the qualities of luminescence, transparency, movement and connectivity are transferred from projected images to the surfaces on which they are projected and the spaces around them; and third, an examination of the ways that sleepwalkers uses only certain aspects of narrativity, those concerned with movement and change, and avoids hermeneutic absorption in order to keep the spectators moving (transposing the idea of sleepwalking from characters to spectators). Transience and transparency are key ideas in the conceptualisation of the work, and these are deployed with significant differences in relation to the distinctive characteristics of each city and each museum.

Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

Sociality and money

This is a translation of ‘Socialité et argent’, a text by Emmanuel Levinas originally published in 1987. Levinas describes the emergence of money out of interhuman relations of exchange and the social relations – sociality – that result. While elsewhere he has presented sociality as ‘nonindifference to alterity’ it appears here as ‘proximity of the stranger’ and points to the tension between an economic system based on money and the basic human disposition to respond to the face of the other person. Money both encodes and effaces sociality, both designates and disguises social relations. It arises from the way that needs and interests are manifested in exchange relations, in what he calls the ‘interestedness’ of economic life. But interests are always already cut through by the fact that being is always ‘being with others’. Being is always ‘interbeing’. Interestedness is always confronted by disinterestedness, that is, by a sociality marked by the ‘goodness of giving’, attachment to and concern for the poverty of the other person. Levinas concludes with a discussion of sociality and justice, posing questions about the tension between the demand to respond to an Other immediately before me and at the same time to respond to the demands of an other Other (the third person) who also invites a response.

Réflexions sur le ‘Nucléaire interdit'

A discussion of the taboo on nuclear use from the perspective of different governments, focusing on the circumstances of the post-Cold War environment where the danger of nuclear proliferation looms large.

Late Pleistocene climate change and the global expansion of anatomically modern humans

The extent to which past climate change has dictated the pattern and timing of the out-of-Africa expansion by anatomically modern humans is currently unclear [Stewart JR, Stringer CB (2012) Science 335:1317–1321]. In particular, the incompleteness of the fossil record makes it difficult to quantify the effect of climate. Here, we take a different approach to this problem; rather than relying on the appearance of fossils or archaeological evidence to determine arrival times in different parts of the world, we use patterns of genetic variation in modern human populations to determine the plausibility of past demographic parameters. We develop a spatially explicit model of the expansion of anatomically modern humans and use climate reconstructions over the past 120 ky based on the Hadley Centre global climate model HadCM3 to quantify the possible effects of climate on human demography. The combinations of demographic parameters compatible with the current genetic makeup of worldwide populations indicate a clear effect of climate on past population densities. Our estimates of this effect, based on population genetics, capture the observed relationship between current climate and population density in modern hunter–gatherers worldwide, providing supporting evidence for the realism of our approach. Furthermore, although we did not use any archaeological and anthropological data to inform the model, the arrival times in different continents predicted by our model are also broadly consistent with the fossil and archaeological records. Our framework provides the most accurate spatiotemporal reconstruction of human demographic history available at present and will allow for a greater integration of genetic and archaeological evidence.

Postglacial vegetation, fire and climate dynamics at Central Chilean Patagonia (Lake Shaman, 44ºS)

A 19 cal ka BP pollen and charcoal record from Lake Shaman (44°S; 71°W, Chile) was analyzed to establish vegetation, fire and climate dynamics of the forest-steppe ecotone in Central Chilean Patagonia. Lake Shaman record indicates that the upper Río Cisnes valley was free of ice at around 19 cal ka BP. From this date and until 14.8 cal ka BP, a grass steppe with high proportions of shrubs associated to colder and drier conditions than present developed in this area. A continuous increase of Nothofagus accompanied by a decline in the steppe shrubs and sudden dominance of paludal over aquatic plants from 11 cal ka BP was associated to effective moisture increase but still under modern values. The replacement of the cold-dry grass-shrub steppe by a similar-than-present forest-steppe ecotone suggests an increase in temperature indicating the onset of the Holocene. At the same time, moderate fire activity suggested by the charcoal record could be related to major fuel availability as consequence of Nothofagus forest expansion. Between 8 and 3 cal ka BP, the record indicates the easternmost position of the forest-steppe ecotone suggesting the highest effective moisture with the establishment of seasonality between 5 and 3 cal ka BP. From 3 cal ka BP, the record indicates a retraction of the forest-steppe ecotone accompanied by a high pollen record variability and an increased fire activity. These late changes suggest decreased effective moisture associated with a high climatic variability. At regional and extra-regional scale, climatic changes at Lake Shaman's record are mostly associated to changes (latitudinal shifts and/or strengthening/weakening) of past Southern Westerlies that were previously recorded along Patagonia from the Lateglacial to the mid-Holocene. During the Late Holocene, a regional pattern characterized by high record variability emerges throughout Central Chilean Patagonia. This variability would be related to (1) low magnitude Southern Westerlies changes probably associated to ENSO and/or SAM or (2) the complex relationships between vegetation, fire and human occupations during the last 3 cal ka.

Non-Refoulement between 'Common Article 1' and 'Common Article 3'

This article considers whether, in the context of armed conflicts, certain non-refoulement obligations of non-belligerent States can be derived from the 1949 Geneva Conventions. According to Common Article 1 (CA1) thereof, all High Contracting Parties (HCPs) undertake to ‘respect and to ensure respect’ for the four conventions ‘in all circumstances’. It is contended that CA1 applies both in international armed conflicts (IACs) and in non-international armed conflicts (NIACs). In turn, it is suggested that Common Article 3 (CA3) which regulates conduct in NIACs serves as a ‘minimum yardstick’ also applicable in IACs. It is widely (though not uniformly) acknowledged that the undertaking to ‘ensure respect’ in a given armed conflict extends to HCPs that are not parties to it; nevertheless, the precise scope of this undertaking is subject to scholarly debate. This article concerns situations where, in the course of an (international or non-international) armed conflict, persons ’taking no active part in hostilities’ flee from States where violations of CA3 are (likely to be) occurring to a non-belligerent State. Based on the undertaking in CA1, the central claim of this article is that, as long as risk of exposure to these violations persists, persons should not be refouled notwithstanding possible assessment of whether they qualify as refugees based on the 1951 Refugee Convention definition, or could be eligible for complementary or subsidiary forms of protection that are regulated in regional arrangements. The analysis does not affect the explicit protection from refoulement that the Fourth Geneva Convention accords to ‘protected persons’ (as defined in Article 4 thereof). It is submitted that CA1 should be read in tandem with other obligations of non-belligerent States under the 1949 Geneva Conventions. Most pertinently, all HCPs are required to take specific measures to repress ‘grave breaches’ and to take measures necessary for the suppression of all acts contrary to the 1949 Geneva Conventions other than the grave breaches. A HCP that is capable of protecting displaced persons from exposure to risks of violations of CA3 and nonetheless refoules them to face such risks is arguably failing to take lawful measures at its disposal in order to suppress acts contrary to the conventions and, consequently, fails to ‘ensure respect’ for the conventions. KEYWORDS Non-refoulement; International Armed Conflict; Non-International Armed Conflict; Common Article 1; Common Article 3

Extension of the TAMSAT satellite-based rainfall monitoring over Africa and from 1983 to present

Tropical Applications of Meteorology Using Satellite Data and Ground-Based Observations (TAMSAT) rainfall monitoring products have been extended to provide spatially contiguous rainfall estimates across Africa. This has been achieved through a new, climatology-based calibration, which varies in both space and time. As a result, cumulative estimates of rainfall are now issued at the end of each 10-day period (dekad) at 4-km spatial resolution with pan-African coverage. The utility of the products for decision making is improved by the routine provision of validation reports, for which the 10-day (dekadal) TAMSAT rainfall estimates are compared with independent gauge observations. This paper describes the methodology by which the TAMSAT method has been applied to generate the pan-African rainfall monitoring products. It is demonstrated through comparison with gauge measurements that the method provides skillful estimates, although with a systematic dry bias. This study illustrates TAMSAT’s value as a complementary method of estimating rainfall through examples of successful operational application.