Synthesis and characterization of star polymers and cross-linked star polymer model networks with cores based on an asymmetric, hydrolyzable dimethacrylate cross-linker

A hydrolyzable dimethacrylate cross-linker, 2-methyl-2,4-pentanediol dimethacrylate (MPDMA), was synhesized by the reaction of 2-methyl-2,4-pentanediol and methacryloyl chloride in the presence of triethylamine. This cross-linker was used to prepare a neat cross-linker network and three cross-linked star polymer model networks (CSPMNs) of methyl methacrylate (MMA), as well as star-shaped polymers of MMA, by group transfer polymerization (GTP). Gel permeation chromatography (GPC) in tetrahydrofuran (THF) confirmed the narrow molecular weight distributions (MWDs) of the linear polymer precursors, and demonstrated the increase in molecular weight (MW) on each successive addition of cross-linker or monomer. Characterization of the star polymers by static light scattering (SLS) in THF showed that star polymers with MPDMA cores bear a relatively small number of arms, between 7 and 35. All star polymers and polymer networks containing the MPDMA cross-linker were hydrolyzed at room temperature in neat trifluoroacetic acid to yield lower-MW products.

Synthesis and characterization of star polymers and cross-linked star polymer model networks containing a novel, silicon-based, hydrolyzable cross-linker

An acid-labile dimethacrylate cross-linker, dimethyldi(methacryloyloxy-l-ethoxy)silane (DMDMAES), was synthesized by the reaction of 2-hydroxyethyl methacrylate (HEMA) and dichlorodimethylsilane in the presence of triethylamine. Group transfer polymerization (GTP) was employed to use this cross-linker in the preparation of six hydrolyzable polymer structures: one neat cross-linker network, one randomly cross-linked network of methyl methacrylate (MMA), two star-shaped polymers of MMA, and two cross-linked star polymer model networks (CSPMNs) of MMA. A nonhydrolyzable CSPMN of MMA, based on a stable cross-linker, was also synthesized. Gel permeation chromatography (GPC) in tetrahydrofuran (THF) confirmed the narrow molecular weight distributions (MWDs) of the linear polymer precursors and demonstrated the increase in molecular weight (MW) upon each successive addition of cross-linker or monomer. Characterization by static light scattering (SLS) and GPC showed that star polymers with DMDMAES cores bear a relatively small number of arms, around 7. All star polymers and polymer networks were hydrolyzed using hydrochloric acid in THF. While the MWs of the products from the hydrolysis of the star polymers, the neat cross-linker network, and the randomly cross-linked network were as expected, those from the CSPMNs were of a much higher than expected MW, indicating extensive star-star coupling.

A Vector Approach for the Analysis and Synthesis of Directional Modulation Transmitters

In order to formalize and extend on previous ad-hoc analysis and synthesis methods a theoretical treatment using vector representations of directional modulation (DM) systems is introduced and used to achieve DM transmitter characteristics. An orthogonal vector approach is proposed which allows the artificial orthogonal noise concept derived from information theory to be brought to bear on DM analysis and synthesis. The orthogonal vector method is validated and discussed via bit error rate (BER) simulations.

Challenging the SD benefits attributed to sport Mega-Events hosting

Sport Mega-event hosting faces opposition that is manifested with different intensity during the different phases of the event, from its inception as an idea to its delivery and legacy. Some Social Movements Organisations (SMOs) have acted as indefatigable monitors of the Sustainable Development (SD) dimension of sporting events in general and, in some of the most recent sport mega-events, in particular the Olympics, they have served as important advisors and facilitators. Nevertheless, in many cases we see enthusiastic supporters turning to vehemently challenging whatever positives have been associated with hosting the event. In addition, there is opposition to sport Mega-events in their entirety. That type of opposition tends to employ a holistic prism that manages to identify multiple interconnected negative aspects of hosting a sport mega-event and incorporate them into an anti-systemic discourse. It is important to bear in mind that irrespective of many proclamations to the opposite as far as megas are concerned (projects and/or events), a number of studies have demonstrated that citizen participation and democratic accountability in decision-making have been notoriously absent. After all, the idea of citizen participation in the planning of sport mega-event is essentially the public response to a plan conceived by others. There were, of course, some notable cases of democratic consultation at the early stages of bidding to host a sport mega-event but these more democratic approaches resulted in the failure of the bid (for e.g. Toronto 1996). The knowledge of this by the groups that initiated the hosting idea and the bidding process has led to discouraging in depth public consultation that may fit perfectly to the democratic process but not to the tight schedules of associated projects completion. That produces ‘autocracy against which opposition may arise’ (Hiller, 2000, p. 198). It is this democratic deficit that has led to important instances of social contestation and protest mobilizations by citizen groups as well as the more regular corps of social activists. From a perspective borrowed from the sociology of protest and social movements, sport mega-events hosting can operate as an issue that stimulates protest activities by an existing protest milieu and new actors as well as an important mobilizing resource. In fact, some scholars have also argued that the Olympic Games were an important frame for the transnational activism that was marked by anti-globalization protest in Seattle in 1999 (Cottrell & Nelson, 201; Lenskyj, 2008). In addition, it’s important not to lose sight of other acts dissent that take place in relatively close proximity, about a year before the event when most infrastructural and societal changes brought by hosting the event and impact start to become apparent by the host communities, like the rioting of August 2011 in the London Olympic Boroughs and the 2012 riots of June 2013 in Sao Paulo and other Brazilian cities. This paper starts by outlining the SD claims made in the bidding to host the summer Olympic Games by five prospective hosts (Sydney; Athens; Beijing; London and Rio) proceeds towards examining the opposition and challenges that was manifested in relation to these claims. In Particular it provides an assessment of protest-events over the aforementioned different phases of sport mega-events hosting. A different picture emerges for each of the host nation that is partly explained by local, national and global configuration of protest politics. Whereas the post-event legacy of the first two hosts of the Games can be assessed and that way see the validity of claims made by challengers in the other phases, in the other three cases, the implementation of Olympic Games Impact (OGI) studies offers the tool for discussing the post-event phase for Beijing and London and engage in a speculative exercise for the case of Rio. Judging by available findings, the paper concludes that the SD aspiration made in the bid documents are unlikely to be met and social contestation based on the same issues is likely to increase due to the current global economic crisis and BRICS, like China and Brazil, having entered the process of becoming global economic hegemons.

Presence of cave bears in western Austria before the onset of the Last Glacial Maximum: new radiocarbon dates and palaeoclimatic considerations

Tischoferhohle and Pendling-Barenhohle near Kufstein, Tyrol, are among the only locations where remains of cave bear, Ursus spelaeus-group, were found in the western part of Austria. One sample from each site was radiocarbon-dated four decades ago to ca. 28 C-14 ka BP. Here we report that attempts to date additional samples from Pendling-Barenhohle have failed due to the lack of collagen, casting doubts on the validity of the original measurement. We also unsuccessfully tried to date flowstone clasts embedded in the bone-bearing sediment to provide maximum constraints on the age of this sediment. Ten cave bear bones from Tischoferhohle showing good collagen preservation were radiocarbon-dated to 31.1-39.9 C-14 ka BP, again pointing towards an age underestimation by the original radiocarbon-dated sample from this site. These new dates from Tischoferhohle are therefore currently the only reliable cave bear dates in western Austria and constrain the interval of cave occupation to 44.3-33.5 cal ka BP. We re-calibrate and re-evaluate dates of alpine cave bear samples in the context of available palaeoclimate information from the greater alpine region covering the transition into the Last Glacial Maximum, eventually leading to the demise of this megafauna.

Summary of the Snowmastodon Project Special Volume: A high-elevation, multi-proxy biotic and environmental record of MIS 6-4 from the Ziegler Reservoir fossil site, Snowmass Village, Colorado, USA

In North America, terrestrial records of biodiversity and climate change that span Marine Oxygen Isotope Stage (MIS) 5 are rare. Where found, they provide insight into how the coupling of the ocean-atmosphere system is manifested in biotic and environmental records and how the biosphere responds to climate change. In 2010-2011, construction at Ziegler Reservoir near Snowmass Village, Colorado (USA) revealed a nearly continuous, lacustrine/wetland sedimentary sequence that preserved evidence of past plant communities between similar to 140 and 55 lea, including all of MIS 5. At an elevation of 2705 m, the Ziegler Reservoir fossil site also contained thousands of well-preserved bones of late Pleistocene megafauna, including mastodons, mammoths, ground sloths, horses, camels, deer, bison, black bear, coyotes, and bighorn sheep. In addition, the site contained more than 26,000 bones from at least 30 species of small animals including salamanders, otters, muskrats, minks, rabbits, beavers, frogs, lizards, snakes, fish, and birds. The combination of macro- and micro-vertebrates, invertebrates, terrestrial and aquatic plant macrofossils, a detailed pollen record, and a robust, directly dated stratigraphic framework shows that high-elevation ecosystems in the Rocky Mountains of Colorado are climatically sensitive and varied dramatically throughout MIS 5 

Crime, Punishment and Article 3 ECHR: Puzzles and Prospects of Applying an Absolute Right in a Penal Context

Article 3 of the European Convention on Human Rights (ECHR), which provides that ‘No one shall be subjected to torture or to inhuman or degrading treatment or punishment’, is considered to enshrine an absolute right. Yet it contains an under-explored element: inhuman and degrading punishment. While torture has been the subject of extensive academic commentary, and inhuman and degrading treatment has been examined to some extent, the prohibition of inhuman and degrading punishment has not been explored in significant depth, in spite of its considerable potential to alter the penal landscape.

This paper elucidates the key doctrinal elements of inhuman and degrading punishment ‘and treatment associated with it’, in the words of the European Court of Human Rights (ECtHR). It addresses a number of ‘puzzles’ or problems which arise in applying the absolute right enshrined in Article 3 of the ECHR to sentencing and imprisonment, clarifies ECtHR doctrine and highlights some of its key implications. Bringing a theoretically informed understanding to bear on the application of Article 3 of the ECHR in a penal context, the paper provides clarity and coherence to a complex and crucial intersection between human rights and penology.

VIEWING LEED PATTERNS AS ELECTRON HOLOGRAMS

It is shown theoretically that LEED patterns from ordered overlayer systems bear a strong relationship to electron holograms, and that phase information is recorded in the diffraction intensities. It is, therefore, possible to obtain structural information by direct holographic inversion from conventional LEED I-V spectra.

A Burkholderia Type VI Effector Deamidates Rho GTPases to Activate the Pyrin Inflammasome

Burkholderia cenocepacia is an opportunistic pathogen of the cystic fibrosis lung that elicits a strong inflammatory response. B. cenocepacia employs a type VI secretion system (T6SS) to survive in macrophages by disarming Rho-type GTPases, causing actin cytoskeletal defects. Here, we identified TecA, a non-VgrG T6SS effector responsible for actin disruption. TecA and other bacterial homologs bear a cysteine protease-like catalytic triad, which inactivates Rho GTPases by deamidating a conserved asparagine in the GTPase switch-I region. RhoA deamidation induces caspase-1 inflammasome activation, which is mediated by the familial Mediterranean fever disease protein Pyrin. In mouse infection, the deamidase activity of TecA is necessary and sufficient for B. cenocepacia-triggered lung inflammation and also protects mice from lethal B. cenocepacia infection. Therefore, Burkholderia TecA is a T6SS effector that modifies a eukaryotic target through an asparagine deamidase activity, which in turn elicits host cell death and inflammation through activation of the Pyrin inflammasome.