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This article introduces the juxtaposed notions of liberal and neo-liberal gameplay in order to show that, while forms of contemporary game culture are heavily influenced by neo-liberalism, they often appear under a liberal disguise. The argument is grounded in Claus Pias’ idea of games as always a product of their time in terms of economic, political and cultural history. The article shows that romantic play theories (e.g. Schiller, Huizinga and Caillois) are circling around the notion of play as ‘free’, which emerged in parallel with the philosophy of liberalism and respective socio-economic developments such as the industrialization and the rise of the nation state. It shows further that contemporary discourse in computer game studies addresses computer game/play as if it still was the romantic form of play rooted in the paradigm of liberalism. The article holds that an account that acknowledges the neo-liberalist underpinnings of computer games is more suited to addressing contemporary computer games, among which are phenomena such as free to play games, which repeat the structures of a neo-liberal society. In those games the players invest time and effort in developing their skills, although their future value is mainly speculative – just like this is the case for citizens of neo-liberal societies.
Blaise Pascal (1623-1662) gehört zu den größten Geistern, die je auf Erden gelebt haben. Der vorliegende Band versucht eine Verbindungslinie zwischen seiner Rechtsphilosophie und seiner Religionsphilosophie herzustellen, indem er Pascals Gedanken über die Gerechtigkeit zu seiner berühmten Lehre von den drei Ordnungen ins Verhältnis setzt.
Arctic coastal infrastructure and cultural and archeological sites are increasingly vulnerable to erosion and flooding due to amplified warming of the Arctic, sea level rise, lengthening of open water periods, and a predicted increase in frequency of major storms. Mitigating these hazards necessitates decision-making tools at an appropriate scale. The objectives of this paper are to provide such a tool by assessing potential erosion and flood hazards at Herschel Island, a UNESCO World Heritage candidate site. This study focused on Simpson Point and the adjacent coastal sections because of their archeological, historical, and cultural significance. Shoreline movement was analyzed using the Digital Shoreline Analysis System (DSAS) after digitizing shorelines from 1952, 1970, 2000, and 2011. For purposes of this analysis, the coast was divided in seven coastal reaches (CRs) reflecting different morphologies and/or exposures. Using linear regression rates obtained from these data, projections of shoreline position were made for 20 and 50 years into the future. Flood hazard was assessed using a least cost path analysis based on a high-resolution light detection and ranging (LiDAR) dataset and current Intergovernmental Panel on Climate Change sea level estimates. Widespread erosion characterizes the study area. The rate of shoreline movement in different periods of the study ranges from −5.5 to 2.7 m·a⁻¹ (mean −0.6 m·a⁻¹). Mean coastal retreat decreased from −0.6 m·a⁻¹ to −0.5 m·a⁻¹, for 1952–1970 and 1970–2000, respectively, and increased to −1.3 m·a⁻¹ in the period 2000–2011. Ice-rich coastal sections most exposed to wave attack exhibited the highest rates of coastal retreat. The geohazard map combines shoreline projections and flood hazard analyses to show that most of the spit area has extreme or very high flood hazard potential, and some buildings are vulnerable to coastal erosion. This study demonstrates that transgressive forcing may provide ample sediment for the expansion of depositional landforms, while growing more susceptible to overwash and flooding.
Fruits exhibit a vast array of different 3D shapes, from simple spheres and cylinders to more complex curved forms; however, the mechanism by which growth is oriented and coordinated to generate this diversity of forms is unclear. Here, we compare the growth patterns and orientations for two very different fruit shapes in the Brassicaceae: the heart-shaped Capsella rubella silicle and the near-cylindrical Arabidopsis thaliana silique. We show, through a combination of clonal and morphological analyses, that the different shapes involve different patterns of anisotropic growth during three phases. These experimental data can be accounted for by a tissue level model in which specified growth rates vary in space and time and are oriented by a proximodistal polarity field. The resulting tissue conflicts lead to deformation of the tissue as it grows. The model allows us to identify tissue-specific and temporally specific activities required to obtain the individual shapes. One such activity may be provided by the valve-identity gene FRUITFULL, which we show through comparative mutant analysis to modulate fruit shape during post-fertilisation growth of both species. Simple modulations of the model presented here can also broadly account for the variety of shapes in other Brassicaceae species, thus providing a simplified framework for fruit development and shape diversity.
The speciation of 2-Mercaptopyridine in aqueous solution has been investigated with nitrogen 1s Near Edge X-ray Absorption Fine Structure spectroscopy and time dependent Density Functional Theory. The prevalence of distinct species as a function of the solvent basicity is established. No indications of dimerization towards high concentrations are found. The determination of different molecular structures of 2-Mercaptopyridine in aqueous solution is put into the context of proton-transfer in keto-enol and thione-thiol tautomerisms. (C) 2016 The Authors. Published by Elsevier B.V.
The agricultural transition profoundly changed human societies. We sequenced and analysed the first genome (1.39x) of an early Neolithic woman from Ganj Dareh, in the Zagros Mountains of Iran, a site with early evidence for an economy based on goat herding, ca. 10,000 BP. We show that Western Iran was inhabited by a population genetically most similar to hunter-gatherers from the Caucasus, but distinct from the Neolithic Anatolian people who later brought food production into Europe. The inhabitants of Ganj Dareh made little direct genetic contribution to modern European populations, suggesting those of the Central Zagros were somewhat isolated from other populations of the Fertile Crescent. Runs of homozygosity are of a similar length to those from Neolithic farmers, and shorter than those of Caucasus and Western Hunter-Gatherers, suggesting that the inhabitants of Ganj Dareh did not undergo the large population bottleneck suffered by their northern neighbours. While some degree of cultural diffusion between Anatolia, Western Iran and other neighbouring regions is possible, the genetic dissimilarity between early Anatolian farmers and the inhabitants of Ganj Dareh supports a model in which Neolithic societies in these areas were distinct.
The coil-to-globule transition of poly(N-isopropylacrylamide) (PNIPAM) microgel particles suspended in water has been investigated in situ as a function of heating and cooling rate with four optical process analytical technologies (PAT), sensitive to structural changes of the polymer. Photon Density Wave (PDW) spectroscopy, Focused Beam Reflectance Measurements (FBRM), turbidity measurements, and Particle Vision Microscope (PVM) measurements are found to be powerful tools for the monitoring of the temperature-dependent transition of such thermo-responsive polymers. These in-line technologies allow for monitoring of either the reduced scattering coefficient and the absorption coefficient, the chord length distribution, the reflected intensities, or the relative backscatter index via in-process imaging, respectively. Varying heating and cooling rates result in rate-dependent lower critical solution temperatures (LCST), with different impact of cooling and heating. Particularly, the data obtained by PDW spectroscopy can be used to estimate the thermodynamic transition temperature of PNIPAM for infinitesimal heating or cooling rates. In addition, an inverse hysteresis and a reversible building of micrometer-sized agglomerates are observed for the PNIPAM transition process.
More effort — more results
(2016)
The development of 'omics' technologies has progressed to address complex biological questions that underlie various plant functions thereby producing copious amounts of data. The need to assimilate large amounts of data into biologically meaningful interpretations has necessitated the development of statistical methods to integrate multidimensional information. Throughout this review, we provide examples of recent outcomes of 'omics' data integration together with an overview of available statistical methods and tools.
Mountain and upland regions provide a wide range of ecosystem services to residents and visitors. While ecosystem research in mountain regions is on the rise, the linkages between sociocultural benefits and ecological systems remain little explored. Mountainous regions close to urban areas provide numerous benefits to a large number of individuals, suggesting a high social value, particularly for cultural ecosystem services. We explored and compared visitors' valuation of ecosystem services in the Pentland Hills, an upland range close to the city of Edinburgh, Scotland, and urban green spaces within Edinburgh. Based on 715 responses to user surveys in both study areas, we identified intense use and high social value for both areas. Several ecosystem services were perceived as equally important in both areas, including many cultural ecosystem services. Significant differences were revealed in the value of physically using nature, which Pentland Hills users rated more highly than those in the urban green spaces, and of mitigation of pollutants and carbon sequestration, for which the urban green spaces were valued more highly. Major differences were further identified for preferences in future land management, with nature-oriented management preferred by about 57% of the interviewees in the Pentland Hills, compared to 31% in the urban parks. The study highlights the substantial value of upland areas in close vicinity to a city for physically using and experiencing nature, with a strong acceptance of nature conservation.
Ecosystem services have a significant impact on human wellbeing. While ecosystem services are frequently represented by monetary values, social values and underlying social benefits remain under explored. The purpose of this study is to assess whether and how social benefits have been explicitly addressed within socio-economic and socio-cultural ecosystem services research, ultimately allowing a better understanding between ecosystem services and human well-being. In this paper, we reviewed 115 international primary valuation studies and tested four hypotheses associated to the identification of social benefits of ecosystem services using logistic regressions. Tested hypotheses were that (1) social benefits are mostly derived in studies that assess cultural ecosystem services as opposed to other ecosystem service types, (2) there is a pattern of social benefits and certain cultural ecosystem services assessed simultaneously, (3) monetary valuation techniques go beyond expressing monetary values and convey social benefits, and (4) directly addressing stakeholder's views the consideration of social benefits in ecosystem service assessments. Our analysis revealed that (1) a variety of social benefits are valued in studies that assess either of the four ecosystem service types, (2) certain social benefits are likely to co-occur in combination with certain cultural ecosystem services, (3) of the studies that employed monetary valuation techniques, simulated market approaches overlapped most frequently with the assessment of social benefits and (4) studies that directly incorporate stakeholder's views were more likely to also assess social benefits. (C) 2016 Elsevier B.V. All rights reserved.
The outermost cell layer of plants, the epidermis, and its outer (lateral) membrane domain facing the environment are continuously challenged by biotic and abiotic stresses. Therefore, the epidermis and the outer membrane domain provide important selective and protective barriers. However, only a small number of specifically outer membrane-localized proteins are known. Similarly, molecular mechanisms underlying the trafficking and the polar placement of outer membrane domain proteins require further exploration. Here, we demonstrate that ACTIN7 (ACT7) mediates trafficking of the PENETRATION3 (PEN3) outer membrane protein from the trans-Golgi network (TGN) to the plasma membrane in the root epidermis of Arabidopsis (Arabidopsis thaliana) and that actin function contributes to PEN3 endocytic recycling. In contrast to such generic ACT7-dependent trafficking from the TGN, the EXOCYST84b (EXO84b) tethering factor mediates PEN3 outer-membrane polarity. Moreover, precise EXO84b placement at the outer membrane domain itself requires ACT7 function. Hence, our results uncover spatially and mechanistically distinct requirements for ACT7 function during outer lateral membrane cargo trafficking and polarity establishment. They further identify an exocyst tethering complex mediator of outer lateral membrane cargo polarity.
The UN sustainable development goals contain environmental, economic, and social objectives. They may only be reached, or at least it would be easier to reach them, if instead of a trade-off between these objectives that implies a need for balancing them, there are synergies to be reaped. This paper discusses how the structures of economic models typically used in policy analysis influence whether win-win strategies for the environment and the economy can be conceptualised and analysed. With a focus on climate policy modelling, the paper points out how, by construction, commonly used model structures find mitigation costs rather than benefits. This paper describes mechanisms that, when added to these model structures, can bring win- win options into a model's solution horizon, and which provide a spectrum of alternative modelling approaches that allow for the identification of such options.
The enormous species richness of flowering plants is at least partly due to floral diversification driven by interactions between plants and their animal pollinators [1, 2]. Specific pollinator attraction relies on visual and olfactory floral cues [3-5]; floral scent can not only attract pollinators but also attract or repel herbivorous insects [6-8]. However, despite its central role for plant-animal interactions, the genetic control of floral scent production and its evolutionary modification remain incompletely understood [9-13]. Benzenoids are an important class of floral scent compounds that are generated from phenylalanine via several enzymatic pathways [14-17]. Here we address the genetic basis of the loss of floral scent associated with the transition from outbreeding to selfing in the genus Capsella. While the outbreeding C. grandiflora emits benzaldehyde as a major constituent of its floral scent, this has been lost in the selfing C. rubella. We identify the Capsella CNL1 gene encoding cinnamate: CoA ligase as responsible for this variation. Population genetic analysis indicates that CNL1 has been inactivated twice independently in C. rubella via different novel mutations to its coding sequence. Together with a recent study in Petunia [18], this identifies cinnamate: CoA ligase as an evolutionary hotspot for mutations causing the loss of benzenoid scent compounds in association with a shift in the reproductive strategy of Capsella from pollination by insects to self-fertilization.
Turkey has been severely affected by many natural hazards, in particular earthquakes and floods. Although there is a large body of literature on earthquake hazards and risks in Turkey, comparatively little is known about flood hazards and risks. Therefore, with this study it is aimed to investigate flood patterns, societal and economic impacts of flood hazards in Turkey, as well as providing a comparative overview of the temporal and spatial distribution of flood losses by analysing EM-DAT (Emergency Events Database) and TABB (Turkey Disaster Data Base) databases on disaster losses throughout Turkey for the years 1960-2014. The comparison of these two databases reveals big mismatches of the flood data, e.g. the reported number of events, number of affected people and economic loss, differ dramatically. With this paper, it has been explored reasons for mismatches. Biases and fallacies for loss data in the two databases has been discussed as well. Since loss data collection is gaining more and more attention, e.g. in the Sendai Framework for Disaster Risk Reduction 2015-2030 (SFDRR), the study could offer a base-work for developing guidelines and procedures on how to standardize loss databases and implement across the other hazard events, as well as substantial insights for flood risk mitigation and adaptation studies in Turkey and will offer valuable insights for other (European) countries.
Since the economic crisis in 2008, European youth unemployment rates have been persistently high at around 20% on average. The majority of European countries spends significant resources each year on active labor market programs (ALMP) with the aim of improving the integration prospects of struggling youths. Among the most common programs used are training courses, job search assistance and monitoring, subsidized employment, and public work programs. For policy makers, it is of upmost importance to know which of these programs work and which are able to achieve the intended goals – may it be the integration into the first labor market or further education. Based on a detailed assessment of the particularities of the youth labor market situation, we discuss the pros and cons of different ALMP types. We then provide a comprehensive survey of the recent evidence on the effectiveness of these ALMP for youth in Europe, highlighting factors that seem to promote or impede their effectiveness in practice. Overall, the findings with respect to employment outcomes are only partly promising. While job search assistance (with and without monitoring) results in overwhelmingly positive effects, we find more mixed effects for training and wage subsidies, whereas the effects for public work programs are clearly negative. The evidence on the impact of ALMP on furthering education participation as well as employment quality is scarce, requiring additional research and allowing only limited conclusions so far.
We show that self-consistent partial synchrony in globally coupled oscillatory ensembles is a general phenomenon. We analyze in detail appearance and stability properties of this state in possibly the simplest setup of a biharmonic Kuramoto-Daido phase model as well as demonstrate the effect in limit-cycle relaxational Rayleigh oscillators. Such a regime extends the notion of splay state from a uniform distribution of phases to an oscillating one. Suitable collective observables such as the Kuramoto order parameter allow detecting the presence of an inhomogeneous distribution. The characteristic and most peculiar property of self-consistent partial synchrony is the difference between the frequency of single units and that of the macroscopic field.
Zur Wiedergutmachung nationalsozialistischen Unrechts garantiert Art. 116 Abs. 2 GG Abkömmlingen von in diskriminierender Weise ausgebürgerten Deutschen die deutsche Staatsangehörigkeit. Dadurch soll der Zustand wiederhergestellt werden, der ohne die Ausbürgerung bestehen würde. Daher wird insoweit regelmäßig auf das geltende Staatsangehörigkeitsrecht abgestellt. § 4 Abs. 4 StAG hat im Jahr 2000 eine Beschränkung der Weitergabe der deutschen Staatsangehörigkeit für im Ausland geborene Kinder deutscher Staatsangehöriger eingeführt, die selbst bereits im Ausland geboren wurden. Dadurch wird möglicherweise der Anwendungsbereich des Art. 116 Abs. 2 GG dauerhaft signifikant eingeschränkt; unter Umständen wird die Norm gar obsolet. Vor diesem Hintergrund wird das Spannungsverhältnis zwischen der uneingeschränkten Anwendung des § 4 Abs. 4 StAG mit dem verfassungsrechtlich verbürgerten Recht auf Wiedereinbürgerung von Kindern zu Unrecht ausgebürgerter Deutscher erörtert.
In November 2015, the 14th Session of the Assembly of States Parties to the Rome Statute of the International Criminal Court (ICC) adopted, by consensus, an amendment providing for the deletion of Article 124 of the ICC Statute, which so far enables contracting parties, when joining the Statute, to opt out from the ICC’s treaty-based war crimes-related jurisdiction. After considering the genesis of the provision and the practice arising under Article 124 of the ICC Statute so far, this article considers the arguments for and against the deletion of Article 124 in light of the increasingly small number of accessions to the ICC Statute that have been forthcoming in the last few years. It also analyses the quite strict requirements for the entry into force of the amendment, as well as the effect of the entry into force of the amendment on possible declarations having been made pending such entry into force. It ends by considering the positive effect a continued applicability of Article 124 may have on states so far being reluctant to accede to the ICC Statute.
Low Earth orbiting geomagnetic satellite missions, such as the Swarm satellite mission, are the only means to monitor and investigate ionospheric currents on a global scale and to make in situ measurements of F region currents. High-precision geomagnetic satellite missions are also able to detect ionospheric currents during quiet-time geomagnetic conditions that only have few nanotesla amplitudes in the magnetic field. An efficient method to isolate the ionospheric signals from satellite magnetic field measurements has been the use of residuals between the observations and predictions from empirical geomagnetic models for other geomagnetic sources, such as the core and lithospheric field or signals from the quiet-time magnetospheric currents. This study aims at highlighting the importance of high-resolution magnetic field models that are able to predict the lithospheric field and that consider the quiet-time magnetosphere for reliably isolating signatures from ionospheric currents during geomagnetically quiet times. The effects on the detection of ionospheric currents arising from neglecting the lithospheric and magnetospheric sources are discussed on the example of four Swarm orbits during very quiet times. The respective orbits show a broad range of typical scenarios, such as strong and weak ionospheric signal (during day- and nighttime, respectively) superimposed over strong and weak lithospheric signals. If predictions from the lithosphere or magnetosphere are not properly considered, the amplitude of the ionospheric currents, such as the midlatitude Sq currents or the equatorial electrojet (EEJ), is modulated by 10–15 % in the examples shown. An analysis from several orbits above the African sector, where the lithospheric field is significant, showed that the peak value of the signatures of the EEJ is in error by 5 % in average when lithospheric contributions are not considered, which is in the range of uncertainties of present empirical models of the EEJ.
Over the past ~40 years, several attempts were made to reintroduce Eurasian lynx to suitable habitat within their former distribution range in Western Europe. In general, limited numbers of individuals have been released to establish new populations. To evaluate the effects of reintroductions on the genetic status of lynx populations we used 12 microsatellite loci to study lynx populations in the Bohemian–Bavarian and Vosges–Palatinian forests. Compared with autochthonous lynx populations, these two reintroduced populations displayed reduced genetic diversity, particularly the Vosges–Palatinian population. Our genetic data provide further evidence to support the status of ‘endangered’ and ‘critically endangered’ for the Bohemian–Bavarian and Vosges–Palatinian populations, respectively. Regarding conservation management, we highlight the need to limit poaching, and advocate additional translocations to bolster genetic variability.
The current study investigates an interaction between numbers and physical size (i.e. size congruity) in visual search. In three experiments, participants had to detect a physically large (or small) target item among physically small (or large) distractors in a search task comprising single-digit numbers. The relative numerical size of the digits was varied, such that the target item was either among the numerically large or small numbers in the search display and the relation between numerical and physical size was either congruent or incongruent. Perceptual differences of the stimuli were controlled by a condition in which participants had to search for a differently coloured target item with the same physical size and by the usage of LCD-style numbers that were matched in visual similarity by shape transformations. The results of all three experiments consistently revealed that detecting a physically large target item is significantly faster when the numerical size of the target item is large as well (congruent), compared to when it is small (incongruent). This novel finding of a size congruity effect in visual search demonstrates an interaction between numerical and physical size in an experimental setting beyond typically used binary comparison tasks, and provides important new evidence for the notion of shared cognitive codes for numbers and sensorimotor magnitudes. Theoretical consequences for recent models on attention, magnitude representation and their interactions are discussed.
Electrophoretic deposition was used to produce zirconia specimen consisting of alternating layers of fully stabilized cubic zirconia and partially stabilized tetragonal zirconia. In this configuration, the tetragonal stabilized zirconia layers can undergo transformation toughening upon mechanical induced stresses, while the cubic stabilized layers can act as confining element. To understand the volumetric changes due to transformation toughening in these layered materials after indentation, we used an advanced synchrotron-based X-ray mu CT setup and compared the results with surface sensitive methods like Raman spectroscopy, AFM and white light interferometry. The high spatial resolution and the adapted beam energy between the absorption edges of zirconia and yttria allowed discriminating between individual layers due to differences in their yttria content. Furthermore we were able to identify single indents and link volume changes to different physical effects in the different stabilized zirconia parts and visualize the three dimensional volume around only few micrometre sized indents. (C) 2015 Elsevier Ltd. All rights reserved.
The reservoir sediments are important sinks for organic carbon (OC), the OC burial being dependent on two opposite processes, deposition and mineralization. Hence factors such as severe water level fluctuations are expected to influence the rate of OC accumulation as they may affect both deposition and mineralization. The Barasona Reservoir has been historically threatened by siltation, whilst the use of water for irrigation involves a drastic decrease of the water level. In this context, we have studied the physical and chemical characteristics (grain size, major and minor elemental compositions, organic and inorganic carbon, and nitrogen) of the recent sediments of the Barasona Reservoir and the relationships among them in order to: a) elucidate the main processes governing OC accumulation, b) evaluate the rate of OC mineralization and c) approach the effect of drought on the sediment characteristics in this system. Our results indicated that Barasona sediments were dominated by fine silts (>60%) and clays (>20%), the mean particle size decreasing from tail to dam. Desiccation increased particle sorting and size distribution became bimodal, but no effect on average size was observed. Attending to the composition, Barasona sediments were very homogeneous with low concentrations of nitrogen (TN) and phosphorus (<12 g kg(-1) dw and <0.6 g kg(-1) dw, respectively) and high concentration of OC (approximate to 36 kg(-1) dw). TN was negatively related to dry weight Sediment mixing due to drastic changes in water level may have favoured the observed homogeneity of Barasona sediments affecting carbon, major ions and grain size. The high amount of OC deposited in Barasona sediment suggested that the adsorption of OC onto fine particles was more important than in boreal lakes. The rate of oxygen consumption by wet sediment ranged from 2.26 to 3.15 mg O-2 m(-2) day(-1), values close to those compiled for Mediterranean running waters. (C) 2015 Elsevier B.V. All rights reserved.
Regulation alters the characteristics of riversty transforming parts of them into lakes, affecting their hydrology and also the physical, chemical, and biological characteristics and dynamics. Reservoirs have proven to be very effective retaining particulate materials, thereby avoiding the downstream transport of suspended sediment and the chemical substances associated with it (e.g. Carbon, C or Nitrogen, N). The study of fluvial transport of C and N is of great interest since river load represents a major link to the global C and N cycles. Moreover, reservoirs are the most important sinks for organic carbon among inland waters and have a potential significance as nitrogen sinks. In this respect, this paper investigates the effects of a Pyrenean reservoir on the runoff, suspended sediment, C and N derived from the highly active Esera and Isabena rivets. Key findings indicate that the reservoir causes a considerable impact on the Esera-Isabena river fluxes, reducing them dramatically as almost all the inputs are retained within the reservoir. Despite the very dry study year (2011-2012), it can be calculated that almost 300,000 t of suspended sediment were deposited into the Barasona Reservoir, from which more than 16,000 were C (i.e. 2200 t as organic C) and 222 t were N. These values may not be seen as remarkable in a wider global context but, assuming that around 30 hm(3) of sediment are currently stored in the reservoir, figures would increase up to ca. 2.6 x 10(6) t of C (i.e. 360,000 t of organic C) and 35,000 t of N. Nevertheless, these values are indicative and should be treated with caution as there is incomplete understanding of all the processes which affect C and N. Further investigation to establish a more complete picture of C and N yields and budgets by monitoring the different processes involved is essential. (C) 2015 Elsevier B.V. All rights reserved.
Mediterranean climate is characterized by highly irregular rainfall patterns with marked differences between wet and dry seasons which lead to highly variable hydrological fluvial regimes. As a result, and in order to ensure water availability and reduce its temporal variability, a high number of large dams were built during the 20th century (more than 3500 located in Mediterranean rivers). Dams modify the flow regime but also interrupt the continuity of sediment transfer along the river network, thereby changing its functioning as an ecosystem. Within this context, the present paper aims to assess the suspended sediment loads and dynamics of two climatically contrasting Mediterranean regulated rivers (i.e. the Esera and Siurana) during a 2-yr period. Key findings indicate that floods were responsible for 92% of the total suspended sediment load in the River Siurana, while this percentage falls to 70% for the Esera, indicating the importance of baseflows on sediment transport in this river. This fact is related to the high sediment availability, with the Esera acting as a non-supply-limited catchment due to the high productivity of the sources (i.e. badlands). In contrast, the Siurana can be considered a supply-limited system due to its low geomorphic activity and reduced sediment availability, with suspended sediment concentration remaining low even for high magnitude flood events. Reservoirs in both rivers reduce sediment load up to 90%, although total runoff is only reduced in the case of the River Esera. A remarkable fact is the change of the hydrological character of the River Lem downstream for the dam, shifting from a humid mountainous river regime to a quasi-invariable pattern, whereas the Siurana experiences the opposite effect, changing from a flashy Mediterranean river to a more constant flow regime below the dam. (C) 2015 Elsevier B.V. All rights reserved.
EPR spectroscopy is a well suited analytical tool to monitor the electronic situation around paramagnetic metal centres as copper(II) and therefore the structural influences on the paramagnetic ion. 1,2-Dithiosquaratometalates are available by direct synthesis from metal salts with dipotassium-1,2-dithiosquarate and the appropriate counter cations. Synthesis and characterisation of bis(benzyltributylammonium)1,2-dithiosquaratonickelate(II), (BzlBu(3)N)(2)[Ni(dtsq)(2)], and bis(benzyltributylammonium)1,2-dithiosquaratocuprate(II), (BzlBu(3)N)(2)[Cu(dtsq)(2)], with benzyltributylammonium as the counter ion is reported and the X-ray structures of two complexes, (BzlBu(3)N)(2)[Ni(dtsq)(2)] and (BzlBu(3)N)(2)[Cu(dtsq)(2)], are presented. Both complexes, crystallising in the monoclinic space group P2(1)/c, are isostructural with only small differences in the coordination sphere due to the different metal ions. The diamagnetic nickel complex is therefore well suited as a host lattice for the paramagnetic Cu(II) complex to measure EPR for additional structural information. (c) 2015 Institute of Chemistry, Slovak Academy of Sciences
We construct equivariant KK-theory with coefficients in and R/Z as suitable inductive limits over II1-factors. We show that the Kasparov product, together with its usual functorial properties, extends to KK-theory with real coefficients. Let Gamma be a group. We define a Gamma-algebra A to be K-theoretically free and proper (KFP) if the group trace tr of Gamma acts as the unit element in KKR Gamma (A, A). We show that free and proper Gamma-algebras (in the sense of Kasparov) have the (KFP) property. Moreover, if Gamma is torsion free and satisfies the KK Gamma-form of the Baum-Connes conjecture, then every Gamma-algebra satisfies (KFP). If alpha : Gamma -> U-n is a unitary representation and A satisfies property (KFP), we construct in a canonical way a rho class rho(A)(alpha) is an element of KKR/Z1,Gamma (A A) This construction generalizes the Atiyah-Patodi-Singer K-theory class with R/Z-coefficients associated to alpha. (C) 2015 Elsevier Inc. All rights reserved.
The uppermost Cretaceous (upper Campanian-Maastrichtian) marine deposits of the central south Pyrenees host a rich larger benthic foraminiferal fauna and several rudist-rich levels. These marine deposits are directly overlain by the continental facies of the Aren and Tremp Formations, which are famous for their fossil dinosaur remains. Larger benthic foraminiferal distribution documents an important faunal turnover in all the carbonate platform environments within the photic zone, from open marine to littoral areas. Biostratigraphy indicates that this turnover occurred close to the Campanian-Maastrichtian boundary. This is also confirmed by strontium isotope stratigraphy which indicates an earliest Maastrichtian age for the appearance of the larger benthic foraminiferal assemblage constituted by Lepidorbitoides socialis, Clypeorbis mammillata, Wannierina cataluniensis, Orbitoides gruenbachensis, Siderolites aff. calcitrapoides, Fascispira colomi, Omphalocyclus macroporus and Laffiteina mengaudi. In particular, a numerical age of 71 Ma is obtained for the Hippurites radiosus level, just a few meters below the first continental deposits of the Aren sensu stricto Formation. The youngest marine sediments of the central south Pyrenees are early Maastrichtian in age. This is also an important constraint for the age of the end-Cretaceous dinosaur fossil localities of the Tremp basin. (C) 2015 Elsevier Ltd. All rights reserved.
Sarmentofascis zamparelliae n. sp., a new demosponge from the lower Campanian of southern Italy
(2016)
A new coralline sponge, exhibiting typical "stromatoporoid" bodyplan, is described as Sarmentofascis zamparelliae n. sp. from the lower Campanian of the southern Apennines, Italy. It is differentiated from Sarmentofascis cretacea (Turnsek) (Hauterivian of Montenegro) and Sarmentofascis chabrieri Termier, Termier and Vachard (Santonian of France) above all by its slender arborescent skeleton, exhibiting longitudinally distributed astrorhizae-like canals. S. zamparelliae n. sp. is the youngest representative of the genus and is reported from a period exhibiting a distinct decline of "stromatoporoid" sponges. With its clinogonal microstructure and occurrence in inner platform stromatoporoid-foraminiferan floatstones it can be considered a Late Cretaceous environmental analog to the Late Jurassic Cladocoropsis. (C) 2015 Elsevier Ltd. All rights reserved.
The water cycle of sites with shallow groundwater tables is characterized by complex interactions of hydrological and ecological processes. The water balance components, which are subject to diurnal fluctuations, are best measured with groundwater lysimeters. However, the lower boundary condition of such lysimeters affects most of the hydrological variables, particularly when considering short time scales, and has to be defined in such a way as to facilitate realistic simulations. In this paper, different means of controlling the lower boundary condition of groundwater lysimeters were compared with respect to their ability to simulate the behavior of the water balance components properly. Measurements of rain-free periods from a lysimeter station installed in the Spreewald wetland in north-east Germany were evaluated. The most common groundwater lysimeter type is controlled using a Mariotte bottle and sets the groundwater level in the soil monolith to a constant level, which here caused an alteration of the inflow to the lysimeter, with respect to both its value and diurnal behavior. Still, daily evapotranspiration values were realistic and this simple and robust approach may be used for time intervals not shorter than one day. High-resolution measurements can be gained from lysimeters that automatically adjust the groundwater level by a system of pumps and valves on an hourly basis. Still, reliable results were only obtained when the conditions in the lysimeter and the surrounding field, where the target groundwater level was measured, were in accordance. Otherwise (e.g., when the groundwater level differed) an unrealistic inflow behavior evolved. Reasonable results, even for slightly diverging conditions, were gained with a new approach that defined the lower boundary conditions by controlling the inflows and outflows of the lysimeter. This approach further enabled the groundwater level itself to be the study subject, thereby enlarging the field of possible applications of groundwater lysimeters. (C) 2015 Elsevier B.V. All rights reserved.
Socio-political studies in mathematics education often touch complex fields of interaction between education, mathematics and the political. In this paper I present a Foucault-based framework for socio-political studies in mathematics education which may guide research in that area. In order to show the potential of such a framework, I discuss the potential and limits of Marxian ideology critique, present existing Foucault-based research on socio-political aspects of mathematics education, develop my framework and show its use in an outline of a study on socio-political aspects of calculation in the mathematics classroom.
The electrophoretic deposition process was used to produce multi-layered ceramics consisting of alternating layers of fully stabilized cubic zirconia and partially stabilized tetragonal zirconia to make use of their different mechanical behaviour, investigating the possibility to deflect advancing cracks at the interfaces of the different layers. This crack deflection is apparently impacted by a toughening mechanism only found in the tetragonal stabilized zirconia polymorph and is characterized by the stress induced transformation of the metastable tetragonal phase into the monoclinic one, which is accompanied by a volume increase resulting in a closing mechanism for advancing cracks. While improving the electrophoretic deposition process, we investigated the transformation toughening mechanism at the layer interfaces and their effect on crack propagation. Investigations involved a combination of different imaging methods, including light microscopy, white light interferometry, atomic force microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and Raman spectroscopy. (C) 2015 Elsevier Ltd. All rights reserved.
Background & Aims: Exosomes are small membrane vesicles involved in intercellular communication. Hepatocytes are known to release exosomes, but little is known about their biological function. We sought to determine if exosomes derived from hepatocytes contribute to liver repair and regeneration after injury. Methods: Exosomes derived from primary murine hepatocytes were isolated and characterized biochemically and biophysically. Using cultures of primary hepatocytes, we tested whether hepatocyte exosomes induced proliferation of hepatocytes in vitro. Using models of ischemia/reperfusion injury and partial hepatectomy, we evaluated whether hepatocyte exosomes promote hepatocyte proliferation and liver regeneration in vivo. Results: Hepatocyte exosomes, but not exosomes from other liver cell types, induce dose-dependent hepatocyte proliferation in vitro and in vivo. Mechanistically, hepatocyte exosomes directly fuse with target hepatocytes and transfer neutral ceramidase and sphingosine kinase 2 (SK2) causing increased synthesis of sphingosine-1-phosphate (S1P) within target hepatocytes. Ablation of exosomal SK prevents the proliferative effect of exosomes. After ischemia/reperfusion injury, the number of circulating exosomes with proliferative effects increases. Conclusions: Our data shows that hepatocyte-derived exosomes deliver the synthetic machinery to form S1P in target hepatocytes resulting in cell proliferation and liver regeneration after ischemia/reperfusion injury or partial hepatectomy. These findings represent a potentially novel new contributing mechanism of liver regeneration and have important implications for new therapeutic approaches to acute and chronic liver disease. (C) 2015 European Association for the Study of the Liver. Published by Elsevier B.V. All rights reserved.
Allyl, dimethylallyl, crotyl, and prenyl ethers of various aromatic ortho-hydroxy carbonyl compounds undergo a tandem sequence of Claisen rearrangement, carbonyl olefination, and cyclization upon microwave irradiation in the presence of a stabilized ylide. The products are multiply substituted 6- or 8-allylated or prenylated coumarins (2H-chromen-2-ones).
Fossil oyster shells are well-suited to provide palaeotemperature proxies from geologic to seasonal timescales due to their ubiquitous occurrence from Triassic to Quaternary sediments, the seasonal nature of their shell growth and their relative strong resistance to post-mortem alteration. However, the common use to translate calcitic oxygen isotopes into palaeotemperatures is challenged by uncertainties in accounting for past seawater delta O-18, especially in shallow coastal environment where oysters calcify. In principle, the Mg/Ca ratio in oyster shells can provide an alternative palaeothermometer. Several studies provided temperature calibrations for this potential proxy based on modem species, nevertheless their application to palaeo-studies remains hitherto unexplored. Here, we show that past temperature variability in seawater can be obtained from Mg/Ca analyses from selected fossil oyster species and specimens. High-resolution Mg/Ca profiles, combined with delta O-18, were obtained along 41 fossil oyster shells of seven different species from the Palaeogene Proto-Paratethys sea (Central Asia) found in similar as well as different depositional age and environments providing comparison. Suitable Mg/Ca profiles, defined by continuous cyclicity and reproducibility within one shell, are found to be consistent for specimens of the same species but differ systematically between species, implying a dominant species-specific effect on the Mg/Ca signal. Two species studied here (Ostrea (Turkostrea) strictiplicata and Sokolowia buhsii) provide an excellent proxy for palaeoclimate reconstruction from China to Europe in Palaeogene marine sediments. More generally, the protocol developed here can be applied to identify other fossil oyster species suitable for palaeoclimate reconstructions. (C) 2015 Elsevier B.V. All rights reserved.
A link between chemical weathering and physical erosion exists at the catchment scale over a wide range of erosion rates(1,2). However, in mountain environments, where erosion rates are highest, weathering may be kinetically limited(3-5) and therefore decoupled from erosion. In active mountain belts, erosion is driven by bedrock landsliding(6) at rates that depend strongly on the occurrence of extreme rainfall or seismicity(7). Although landslides affect only a small proportion of the landscape, bedrock landsliding can promote the collection and slow percolation of surface runoff in highly fragmented rock debris and create favourable conditions for weathering. Here we show from analysis of surface water chemistry in the Southern Alps of New Zealand that weathering in bedrock landslides controls the variability in solute load of these mountain rivers. We find that systematic patterns in surface water chemistry are strongly associated with landslide occurrence at scales from a single hillslope to an entire mountain belt, and that landslides boost weathering rates and river solute loads over decades. We conclude that landslides couple erosion and weathering in fast-eroding uplands and, thus, mountain weathering is a stochastic process that is sensitive to climatic and tectonic controls on mass wasting processes.
Antarctica’s contribution to global sea-level rise has recently been increasing1. Whether its ice discharge will become unstable and decouple from anthropogenic forcing2,3,4 or increase linearly with the warming of the surrounding ocean is of fundamental importance5. Under unabated greenhouse-gas emissions, ocean models indicate an abrupt intrusion of warm circumpolar deep water into the cavity below West Antarctica’s Filchner–Ronne ice shelf within the next two centuries6,7. The ice basin’s retrograde bed slope would allow for an unstable ice-sheet retreat8, but the buttressing of the large ice shelf and the narrow glacier troughs tend to inhibit such instability9,10,11. It is unclear whether future ice loss will be dominated by ice instability or anthropogenic forcing. Here we show in regional and continental-scale ice-sheet simulations, which are capable of resolving unstable grounding-line retreat, that the sea-level response of the Filchner–Ronne ice basin is not dominated by ice instability and follows the strength of the forcing quasi-linearly. We find that the ice loss reduces after each pulse of projected warm water intrusion. The long-term sea-level contribution is approximately proportional to the total shelf-ice melt. Although the local instabilities might dominate the ice loss for weak oceanic warming12, we find that the upper limit of ice discharge from the region is determined by the forcing and not by the marine ice-sheet instability.
The Puna Plateau, adjacent Eastern Cordillera and the Sierras Pampeanas of the central Andes are largely characterized by thick-skinned, basement-involved deformation. The Puna Plateau hosts similar to N-S trending bedrock ranges bounded by deep-seated reverse faults and sedimentary basins. We contribute to the understanding of thick-skinned dynamics in the Puna Plateau by constraining regional kinematics of the poorly understood southern Puna Plateau through a multidisciplinary approach. On the southeastern plateau, sandstone modal composition and detrital zircon U-Pb and apatite fission-track data from Cenozoic strata indicate basin accumulation during the late Eocene to early Oligocene (similar to 38-28 Ma). Provenance analysis reveals the existence of a regional-scale basin covering the southern Puna Plateau during late Eocene to early Oligocene time (similar to 38-28 Ma) that was sourced from both the western plateau and the eastern plateau margin and had a depocenter located to the west. Petrographic and detrital zircon U-Pb data reveal erosion of proximal western and eastern sources after 12 Ma, in mid-late Miocene time. This indicates that the regional basin was compartmentalized into small-scale depocenters by the growth of basement-cored ranges continuing into the late Miocene (similar to 12-8 Ma). We suggest that the Cenozoic history of the southern Puna Plateau records the formation of a regional basin that was possibly driven by lithospheric flexure during the late Eocene to early Oligocene, before the growth of distributed basement-cored ranges starting as early as the late Oligocene. (C) 2015 Elsevier B.V. All rights reserved.
On the basis of the clinical studies in patients with coronary artery disease (CAD) presenting an increased percentage of activated platelets, we hypothesized that hemocompatibility testing utilizing platelets from healthy individuals may result in an underestimation of the materials' thrombogenicity. Therefore, we investigated the interaction of polymer-based biomaterials with platelets from CAD patients in comparison to platelets from apparently healthy individuals. In vitro static thrombogenicity tests revealed that adherent platelet densities and total platelet covered areas were significantly increased for the low (polydimethylsiloxane, PDMS) and medium (Collagen) thrombogenic surfaces in the CAD group compared to the healthy subjects group. The area per single platelet—indicating the spreading and activation of the platelets—was markedly increased on PDMS treated with PRP from CAD subjects. This could not be observed for collagen or polytetrafluoroethylene (PTFE). For the latter material, platelet adhesion and surface coverage did not differ between the two groups. Irrespective of the substrate, the variability of these parameters was increased for CAD patients compared to healthy subjects. This indicates a higher reactivity of platelets from CAD patients compared to the healthy individuals. Our results revealed, for the first time, that utilizing platelets from apparently healthy donors bears the risk of underestimating the thrombogenicity of polymer-based biomaterials.
New age data have been obtained to time constrain the recent Quaternary volcanism of El Hierro (Canary Islands) and to estimate its recurrence rate. We have carried out Ar-40/Ar-39 geochronology on samples spanning the entire volcanostratigraphic sequence of the island and C-14 geochronology on the most recent eruption on the northeast rift of the island: 2280 +/- 30 yr BP. We combine the new absolute data with a revision of published ages onshore, some of which were identified through geomorphological criteria (relative data). We present a revised and updated chronology of volcanism for the last 33 ka that we use to estimate the maximum eruptive recurrence of the island. The number of events per year determined is 9.7 x 10(-4) for the emerged part of the island, which means that, as a minimum, one eruption has occurred approximately every 1000 years. This highlights the need of more geochronological data to better constrain the eruptive recurrence of El Hierro. (C) 2015 Elsevier Ltd. All rights reserved.
The abandonment of military areas leads to succession processes affecting valuable open-land habitats and is considered to be a major threat for European butterflies. We assessed the ability of hyper spectral remote sensing data to spatially predict the occurrence of one of the most endangered butterfly species (Hipparchia statilinus) in Brandenburg (Germany) on the basis of habitat characteristics at a former military training area. Presence-absence data were sampled on a total area of 36 km(2), and N = 65 adult individuals of Hipparchia statilinus could be detected. The floristic composition within the study area was modeled in a three-dimensional ordination space. Occurrence probabilities for the target species were predicted as niches between ordinated floristic gradients by using Regression Kriging of Indicators. Habitat variance could be explained by up to 81 % with spectral variables at a spatial resolution of 2 x 2 m by transferring PLSR models to imagery. Ordinated ecological niche of Hipparchia statilinus was tested against environmental predictor variables. N = 6 variables could be detected to be significantly correlated with habitat preferences of Hipparchia statilinus. They show that Hipparchia statilinus can serve as a valuable indicator for the evaluation of the conservation status of Natura 2000 habitat type 2330 (inland dunes with open Corynephorus and Agrostis grasslands) protected by the Habitat Directive (Council Directive 92/43/EEC). The authors of this approach, conducted in August 2013 at Doberitzer Heide Germany, aim to increase the value of remote sensing as an important tool for questions of biodiversity research and conservation.
Spatio-temporal control of cellular uptake achieved by photoswitchable cell-penetrating peptides
(2016)
The selective uptake of compounds into specific cells of interest is a major objective in cell biology and drug delivery. By incorporation of a novel, thermostable azobenzene moiety we generated peptides that can be switched optically between an inactive state and an active, cell-penetrating state with excellent spatio-temporal control.
Cross-sectional studies revealed that inclusion of unstable elements in core-strengthening exercises produced increases in trunk muscle activity and thus potential extra stimuli to induce more pronounced performance enhancements in youth athletes. Thus, the purpose of the study was to investigate changes in neuromuscular and athletic performance following core strength training performed on unstable (CSTU) compared with stable surfaces (CSTS) in youth soccer players. Thirty-nine male elite soccer players (age: 17 +/- 1 years) were assigned to two groups performing a progressive core strength-training program for 9 weeks (2-3 times/week) in addition to regular in-season soccer training. CSTS group conducted core exercises on stable (i.e., floor, bench) and CSTU group on unstable (e.g., Thera-Band (R) Stability Trainer, Togu (c) Swiss ball) surfaces. Measurements included tests for assessing trunk muscle strength/activation, countermovement jump height, sprint time, agility time, and kicking performance. Statistical analysis revealed significant main effects of test (pre vs post) for trunk extensor strength (5%, P<0.05, d=0.86), 10-20-m sprint time (3%, P<0.05, d=2.56), and kicking performance (1%, P<0.01, d=1.28). No significant Groupxtest interactions were observed for any variable. In conclusion, trunk muscle strength, sprint, and kicking performance improved following CSTU and CSTS when conducted in combination with regular soccer training.
Acting during phase II metabolism, sulfotransferases (SULTs) serve detoxification by transforming a broad spectrum of compounds from pharmaceutical, nutritional, or environmental sources into more easily excretable metabolites. However, SULT activity has also been shown to promote formation of reactive metabolites that may have genotoxic effects. SULT subtype 1E1 (SULT1E1) was identified as a key player in estrogen homeostasis, which is involved in many physiological processes and the pathogenesis of breast and endometrial cancer. The development of an in silico prediction model for SULT1E1 ligands would therefore support the development of metabolically inert drugs and help to assess health risks related to hormonal imbalances. Here, we report on a novel approach to develop a model that enables prediction of substrates and inhibitors of SULT1E1. Molecular dynamics simulations were performed to investigate enzyme flexibility and sample protein conformations. Pharmacophores were developed that served as a cornerstone of the model, and machine learning techniques were applied for prediction refinement. The prediction model was used to screen the DrugBank (a database of experimental and approved drugs): 28% of the predicted hits were reported in literature as ligands of SULT1E1. From the remaining hits, a selection of nine molecules was subjected to biochemical assay validation and experimental results were in accordance with the in silico prediction of SULT1E1 inhibitors and substrates, thus affirming our prediction hypotheses.
Der vorliegende Beitrag gibt einen Überblick über das Thema „Gewalt an Schulen“ und verknüpft es mit gesundheitlichen Aspekten von Schülerinnen und Schülern. Ausgehend von der Annahme, dass Gewalt und Gesundheit zwei Seiten einer Medaille sind, wird der Frage nachgegangen, wie sich Gewalt- und Mobbingphänomene an deutschen Schulen entwickelt haben und welche Zusammenhänge es zur Gesundheit von Schülerinnen und Schülern gibt. Die empirische Basis bilden langjährige Untersuchungen der Autoren, u. a. im Rahmen der internationalen Studie „Health Behaviour in School-aged Children“ (HBSC). Auf der Basis eigener empirischer Studien werden Prävalenzen und Strukturen der Schülergewalt sowie der Zusammenhang von Gewalt und Gesundheit verdeutlicht und Folgerungen für die Gewalt- und Gesundheitsprävention gezogen. Entgegen dramatisierender Einschätzungen in den Medien zeigt sich, dass in den letzten Jahren eine kontinuierliche Verringerung der Mobbing-Problematik an deutschen Schulen zu verzeichnen ist. Mit Blick auf den Zusammenhang von Gewalt und Gesundheit lässt sich ein signifikanter Zusammenhang zwischen dissozialem Verhalten und Parametern der Gesundheit belegen. So weisen Opfer und Täter-Opfer die größten und Unbeteiligte die geringsten gesundheitlichen Probleme auf, während für Täter – entgegen gängiger Annahmen – eher eine positive Grundstimmung kennzeichnend ist. Aufgrund des engen Zusammenhangs von Gewalt und Gesundheit wird die Folgerung abgeleitet, Gewaltprävention- und Gesundheitsförderung mit Schulentwicklung und Schulprogrammarbeit zu verbinden, um nachhaltige Präventionswirkung zu erzielen.
The article gives an overview of violence at school combined with the health of students. Based on the assumption that violence and health are two sides of the same coin, the article considers the question of the development of violence and bullying phenomena at German schools and its relation to student health. Long-term studies by the authors, such as the international Health Behavior in School-aged Children (HBSC) study, constitute the empirical basis. Prevalence and structures of student violence, as well as the relation between violence and health, are clarified and consequences for the prevention of violence and health are shown on the basis of our own empirical studies. Contrary to dramatic estimates in the media, a continuous reduction of bullying problems at German schools has been registered in recent years. In reference to the relation between violence and health, a significant correlation between dissocial behavior and health parameters was found. Victims and bully-victims show the most health problems and innocent bystanders the least health problems. In contrast to previous findings, bullies show a more positive prevailing mood. Due to the found associations between violence and health, it appears reasonable to combine violence prevention and health promotion measures to achieve sustainable prevention effects.
The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12-tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) ligand, yielding complexes of the general formula [(L-N4Me2)Ru(mu-tape)M(L-N4Me2)](ClO4)(2)(PF6)(2) with M = Fe {[2](ClO4)(2)(PF6)(2)}, Co {[3](ClO4)(2)(PF6)(2)}, and Ni {[4](ClO4)(2)(PF6)(2)}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)- and platinum(II)-dichloride [(bpy)(2)Ru(-tape)PdCl2](PF6)(2) {[5](PF6)(2)} and [(dmbpy)(2)Ru(-tape)PtCl2](PF6)(2) {[6](PF6)(2)}, respectively were also prepared. The molecular structures of the complex cations [2](4+) and [4](4+) were discussed on the basis of the X-ray structures of [2](ClO4)(4)MeCN and [4](ClO4)(4)MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono- and homodinuclear ruthenium(II) complexes of the tape bridging ligand.
Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl) dimethylammonio) propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl) dimethylammonio) propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl) dimethylammonio)butane- 1-sulfonate (SBP) were synthesised and polymerised by reversible addition-fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D2O than in H2O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass. Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments.