Controlled synthesis of poly(neopentyl p-styrene sulfonate) via reversible addition-fragmentation chain transfer polymerisation

The controlled synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) using RAFT polymerisation has been studied. Selected experimental conditions led to the production of PNSS with variable molecular weights and low dispersities (D{stroke}≤1.50). The controlled synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) using reversible addition-fragmentation chain transfer polymerisation has been studied under a wide range of experimental conditions. PNSS can be used as an organic-soluble, thermally labile precursor for industrially valuable poly(p-styrene sulfonate), widely employed in technologies such as ionic exchange membranes and organic electronics. The suitability of two different chain transfer agents, three solvents, three different monomer concentrations and two different temperatures for the polymerisation of neopentyl p-styrene sulfonate is discussed in terms of the kinetics of the process and characteristics of the final polymer. Production of PNSS with systematically variable molecular weights and low dispersities (D{stroke} ≤1.50 in all cases) has been achieved using 2-azidoethyl 2-(dodecylthiocarbonothioylthio)-2-methylpropionate in anisole at 75°C, with an initial monomer concentration of 4.0molL-1. Finally, a poly(neopentyl p-styrene sulfonate)-b-polybutadiene-b-poly(neopentyl p-styrene sulfonate) (PNSS-b-PBD-b-PNSS) triblock copolymer has been synthesised via azide-alkyne click chemistry. Moreover, subsequent thermolysis of the PNSS moieties generated poly(p-styrene sulfonate) end blocks. This strategy allows the fabrication of amphiphilic copolymer films from single organic solvents without the need for post-deposition chemical treatment.

Influencing online grocery innovation:anti-choice as a trigger for activity fragmentation and multi-tasking

This paper reveals how activity fragmentation and multi-tasking become tools of consumer anti-choice in the online grocery sector: facilitated by new technology practices that positively encourage anti-choice. This is demonstrated through five long-term ethnographic case studies of households in the Portsmouth area of England. All the respondents made some form of conscious effort to minimize the amount of time they spent in ‘big box’ grocery stores. They spend more time at home in planning, searching, socializing online, cumulating and fulfilling internet orders than if they had visited a store: something that all could easily do. The findings suggest the need for constant innovation by internet grocers if they are to remain in tune with dynamic consumer lifestyles and advances in technology. Examples of upcoming technologies requiring retailers to re-think their internet strategies are discussed in view of the possibilities offered by activity fragmentation and multi-tasking.

A holistic multi evidence approach to study the fragmentation behaviour of crystalline mannitol

Mannitol is an essential excipient employed in orally disintegrating tablets due to its high palatability. However its fundamental disadvantage is its fragmentation during direct compression, producing mechanically weak tablets. The primary aim of this study was to assess the fracture behaviour of crystalline mannitol in relation to the energy input during direct compression, utilising ball milling as the method of energy input, whilst assessing tablet characteristics of post-milled powders. Results indicated that crystalline mannitol fractured at the hydrophilic (011) plane, as observed through SEM, alongside a reduction in dispersive surface energy. Disintegration times of post-milled tablets were reduced due to the exposure of the hydrophilic plane, whilst more robust tablets were produced. This was shown through higher tablet hardness and increased plastic deformation profiles of the post-milled powders, as observed with a lower yield pressure through an out-of-die Heckel analysis. Evaluation of crystal state using x-ray diffraction/differential scanning calorimetry showed that mannitol predominantly retained the β-polymorph; however x-ray diffraction provided a novel method to calculate energy input into the powders during ball milling. It can be concluded that particle size reduction is a pragmatic strategy to overcome the current limitation of mannitol fragmentation and provide improvements in tablet properties.

Colombian society in the 1990s: Fragmentation, legitimacy, and efficiency

During the nineties, Colombia experienced a two-fold process of restructuring. First, the political system underwent a process of constitutional reform in order to strengthen the state and increase its legitimacy, surpass the exclusionary character of the political regime, and achieve greater equity in the distribution of social resources. Second, the economy made the transition from a Keynesian development strategy to a strategy of “opening” or liberalization and internationalization of the economy, in order to increase the economic efficiency by reducing the “size” of the state and its regulatory role. The purpose of this dissertation is to analyze the interplay and contradictions of economic and political factors in the restructuring of the Colombian politico-economic system. ^ The main finding of this dissertation is that the simultaneous adoption of a neoliberal economic strategy and of the Political Constitution of 1991, have had a contradictory relationship: while the “political opening” has produced favorable conditions for fostering programs of democratization and social integration, the “economic opening” has counteracted that possibility given that it implies a social exclusionary process. This tension has aggravated the problems of political and social integration that have traditionally characterized Colombian society. ^ This crucial tension has also been characteristic of Latin America in the nineties. However, it has been neglected and undertheorized in most of the democratization studies of American comparative politics. Most of them lack consideration of structural aspects. According to those studies, the cause of regime change is determined by the strategic elections of actors. Contrary to these approaches, I develop a structural perspective. I consider that social phenomena are partly determined by structural factors, and scientific research should assign them decisive importance, since a fundamental basis for social action and transformation is to be found in the dynamics of relationships between individuals and structures and the development of contradictions within structures. ^

Life cycle of Deccan trap magma chambers: A crystal scale elemental and strontium isotopic investigation

The Deccan Trap basalts are the remnants of a massive series of lava flows that erupted at the K/T boundary and covered 1-2 million km2 of west-central India. This eruptive event is of global interest because of its possible link to the major mass extinction event, and there is much debate about the duration of this massive volcanic event. In contrast to isotopic or paleomagnetic dating methods, I explore an alternative approach to determine the lifecycle of the magma chambers that supplied the lavas, and extend the concept to obtain a tighter constraint on Deccan’s duration. My method relies on extracting time information from elemental and isotopic diffusion across zone boundaries in individual crystals. I determined elemental and Sr-isotopic variations across abnormally large (2-5 cm) plagioclase crystals from the Thalghat and Kashele “Giant Plagioclase Basalts” from the lowermost Jawhar and Igatpuri Formations respectively in the thickest Western Ghats section near Mumbai. I also obtained bulk rock major, trace and rare earth element chemistry of each lava flow from the two formations. Thalghat flows contain only 12% zoned crystals, with 87 Sr/86Sr ratios of 0.7096 in the core and 0.7106 in the rim, separated by a sharp boundary. In contrast, all Kashele crystals have a wider range of 87Sr/86Sr values, with multiple zones. Geochemical modeling of the data suggests that the two types of crystals grew in distinct magmatic environments. Modeling intracrystalline diffusive equilibration between the core and rim of Thalghat crystals led me to obtain a crystal growth rate of 2.03x10-10 cm/s and a residence time of 780 years for the crystals in the magma chamber(s). Employing some assumptions based on field and geochronologic evidence, I extrapolated this residence time to the entire Western Ghats and obtained an estimate of 25,000–35,000 years for the duration of Western Ghats volcanism. This gave an eruptive rate of 30–40 km3/yr, which is much higher than any presently erupting volcano. This result will remain speculative until a similarly detailed analytical-modeling study is performed for the rest of the Western Ghats formations.

Disturbance Driven Colony Fragmentation as a Driver of a Coral Disease Outbreak

In September of 2010, Brewer's Bay reef, located in St. Thomas (U.S. Virgin Islands), was simultaneously affected by abnormally high temperatures and the passage of a hurricane that resulted in the mass bleaching and fragmentation of its coral community. An outbreak of a rapid tissue loss disease among coral colonies was associated with these two disturbances. Gross lesion signs and lesion progression rates indicated that the disease was most similar to the Caribbean coral disease white plague type 1. Experiments indicated that the disease was transmissible through direct contact between colonies, and five-meter radial transects showed a clustered spatial distribution of disease, with diseased colonies being concentrated within the first meter of other diseased colonies. Disease prevalence and the extent to which colonies were bleached were both significantly higher on unattached colony fragments than on attached colonies, and disease occurred primarily on fragments found in direct contact with sediment. In contrast to other recent studies, disease presence was not related to the extent of bleaching on colonies. The results of this study suggest that colony fragmentation and contact with sediment played primary roles in the initial appearance of disease, but that the disease was capable of spreading among colonies, which suggests secondary transmission is possible through some other, unidentified mechanism.

Arc crust-magma interaction in the Andean Southern Volcanic Zone from thermobarometry, mineral composition, radiogenic isotope and rare earth element systematics of the Azufre-Planchon-Peteroa volcanic complex, Chile

The Andean Southern Volcanic Zone (SVZ) is a vast and complex continental arc that has been studied extensively to provide an understanding of arc-magma genesis, the origin and chemical evolution of the continental crust, and geochemical compositions of volcanic products. The present study focuses on distinguishing the magma/sub-arc crustal interaction of eruptive products from the Azufre-Planchon-Peteroa (APP 35°15'S) volcanic center and other major centers in the Central SVZ (CSVZ 37°S–42°S), Transitional SVZ (TSVZ 34.3–37.0°S), and Northern SVZ (NSVZ 33°S–34°30'S). New Hf and Nd isotopic and trace element data for SVZ centers are consistent with former studies that these magmas experienced variable depths of crystal fractionation, and that crustal assimilation is restricted to the lower crustal depths with an apparent role of garnet. Thermobarometric calculations applied to magma compositions constrain the depth of magma separation from mantle sources in all segments of the SVZ to(70-90 km). Magmatic separation at the APP complex occurs at an average depth of ~50 km which is confined to the mantle lithosphere and the base of the crust suggesting localized thermal abrasion both reservoirs. Thermobarometric calculations indicate that CSVZ primary magmas arise from a similar average depth of (~54 km) which confines magma separation to the asthenospheric mantle. The northwards along-arc Sr-Nd-Hf isotopic data and LREE enrichment accompanied with HREE depletion of SVZ mafic magmas correlates well with northward increasing crustal thickness and decreasing primary melt separation from mantle source regions indicating an increased involvement of lower crustal components in SVZ magma petrogenesis. ^ The study concludes that the development of mature subduction zones over millions of years of continuous magmatism requires that mafic arc derived melts stagnate at lower crustal levels due to density similarities and emplace at lower crustal depths. Basaltic underplating creates localized hot zone environments below major magmatic centers. These regions of high temperature/partial melting, and equilibration with underplated mafic rocks provides the mechanism that controls trace element and isotopic variability of primary magmas of the TSVZ and NSVZ from their baseline CSVZ-like precursors.^

Pollination, Herbivory, and Habitat Fragmentation: Their Effects on the Reproductive Fitness of Angadenia berteroi, a Native Perennial Plant of the South Florida Pine Rocklands

Angadenia berteroi is a tropical perennial subshrub of the pine rocklands with large yellow flowers that set very few fruits. My dissertation seeks to elucidate the factors that affect the reproductive fitness of Angadenia berteroi a native species of the south Florida pine rocklands. I provide novel information on the pollination biology of this native species. I also assess the effects of herbivory on growth and the reproductive success of A. berteroi. Finally, I elucidate how habitat fragmentation and quality are correlated with reproductive fitness of this native perennial plant. Using a novel experimental approach, I determined the most effective pollinator group. I used nylon fishing line of widths corresponding to proboscis diameter of the major groups of visitors to examine pollen removal and deposition. In the field, I estimated visitation frequency and efficacy of each pollinator type. Using potted plants, I exposed flowers to single visit from different types of pollinators to measure fruit set. I performed artificial defoliation with scissors on plants growing in the greenhouse to assess the effects of defoliation before flowering as well as during flowering. Additionally, I used structural equation modelling (SEM) to elucidate how A. berteroi reproductive fitness was affected by habitat fragmentation and quality. My experiments provide evidence that Angadenia berteroi is specialized for bee pollination; though butterflies, skippers and others also visit its flowers, A. berteroi is exclusively pollinated by two native bees of the South Florida pine rocklands . This research also demonstrated that herbivory by the oleander moth may have direct and indirect effects on Angadenia berteroi growth and reproductive success. The SEM results suggested that habitat quality (litter depth and subcanopy cover) may favor reproduction in native species of the South Florida pine rocklands that are properly maintained by periodic fires and exotic control. Insights from this threatened and charismatic species may provide impetus to properly manage remaining pine rocklands in South Florida for this and other endemic understory species.

Conservation ecology of amphibians and reptiles in Sarapiqui, Costa Rica : forest fragmentation and long term population change

In order to explore the conservation ecology of frogs and lizards in the Sarapiqui region of Costa Rica, I compared populations and communities among forest fragments and La Selva Biological Station, as well as across 35 years of sampling at La Selva. Species richness in nine fragments combined was 85% of that found in La Selva, and community composition varied among sites and by fragment size class. Although communities in fragments differed fundamentally from those in intact forest, the high diversity observed across all fragments indicates that preserving a network of small forest patches may be of great conservation value to the herpetofauna of this region. According to data from past studies at La Selva, most common species of leaf-litter frogs and lizards demonstrated significant decreases in density over the 35-year period. My findings may represent either natural population fluctuations or sweeping faunal declines at this site.

Regional Magma Plumbing and emplacement mechanisms of the Faroe-Shetland Sill Complex : Implications for magma transport and petroleum systems within sedimentary basins

Peer reviewed

Regional Magma Plumbing and emplacement mechanisms of the Faroe-Shetland Sill Complex : Implications for magma transport and petroleum systems within sedimentary basins

Peer reviewed

Rise, fragmentation, infringement and fear: emerging urban issues in Chinese clustering in Italy

China is today facing rapid economic development and the long-term implications of China’s rise for European economy, society and culture, are constantly debated but still almost unknown. Moreover, only recently a new volume edited by Kunzmann has clearly pointed out a particular field of research like the EU spatial impact of China’s convergence in the global market. The aim of the present paper is to deal with the spatial issues related to the growing Chinese communities, especially in Italy, that are part of a more general and considerable transformation process of the traditional Chinese enclaves in EU cities: from recognizable “Chinatowns” to new hybrid urban formations where housing, retail, wholesale and even commodity production often tend to match. Key-Concepts like rise, fragmentation, infringement and fear are useful in analysing some of the more controversial socio-economic dynamics of Chinese clusters especially in a traditionally manufactured-based country like Italy, where it’s recognizable a unique paradox of a “double competition” from outside and from inside. This statement poses a serious threat to local economic systems in terms of sustainability and social cohesion, making it necessary to rethink the role and the nature of public action in facing new forms of marginality at urban and regional level.

Effects of protected area downsizing on habitat fragmentation in Yosemite National Park (USA), 1864 – 2014

Protected area downgrading, downsizing, and degazettement (PADDD) has been documented worldwide, but its impacts on biodiversity are poorly understood. To fill this knowledge gap, we reviewed historical documents to identify legal changes that altered the boundaries of Yosemite National Park. We identified two downsizes and five additions between 1905 and 1937 that reduced the size of Yosemite National Park by 30%. To examine the effects of these downsizing events on habitat fragmentation by roads, we compared protected, never-protected, and downsized lands at three spatial scales using four habitat fragmentation metrics: road density, fragment (land surrounded by roads) area-to-perimeter ratio, fragment area, and fragment density. In general, lands that were removed from protection, e.g., downsized, were more highly fragmented than protected lands and indistinguishable from never-protected lands. Lands where downsizes were reversed were less fragmented than lands where downsizes were not reversed. These results suggest that protected area downsizing may exacerbate habitat fragmentation, a key contributor to biodiversity loss globally. Furthermore, the case study in Yosemite National Park demonstrates that iconic protected areas in developed countries are not immune to downsizing. These findings underscore the need to account for PADDD and governance histories in ecological research, monitoring, and evaluation. As we move toward more evidence-based conservation policy, a rigorous understanding of PADDD is essential to ensure that protected areas fulfill their promise as a strategy for conserving global biodiversity.

Fragmentation versus convergence: University students in Brussels and the consumption of TV series on the Internet

info:eu-repo/semantics/published