Modeling the molecular weight distribution of block copolymer formation in a reversible addition-fragmentation chain transfer mediated living radical polymerization

Block copolymers have become an integral part of the preparation of complex architectures through self-assembly. The use of reversible addition-fragmentation chain transfer (RAFT) allows blocks ranging from functional to nonfunctional polymers to be made with predictable molecular weight distributions. This article models block formation by varying many of the kinetic parameters. The simulations provide insight into the overall polydispersities (PDIs) that will be obtained when the chain-transfer constants in the main equilibrium steps are varied from 100 to 0.5. When the first dormant block [polymer-S-C(Z)=S] has a PDI of 1 and the second propagating radical has a low reactivity to the RAFT moiety, the overall PDI will be greater than 1 and dependent on the weight fraction of each block. When the first block has a PDI of 2 and the second propagating radical has a low reactivity to the RAFT moiety, the PDI will decrease to around 1.5 because of random coupling of two broad distributions. It is also shown how we can in principle use only one RAFT agent to obtain block copolymers with any desired molecular weight distribution. We can accomplish this by maintaining the monomer concentration at a constant level in the reactor over the course of the reaction. (c) 2005 Wiley Periodicals, Inc.

The effect of caudal block on functional residual capacity and ventilation homogeneity in healthy children

Caudal block results in a motor blockade that can reduce abdominal wall tension. This could interact with the balance between chest wall and lung recoil pressure and tension of the diaphragm, which determines the static resting volume of the lung. On this rationale, we hypothesised that caudal block causes an increase in functional residual capacity and ventilation distribution in anaesthetised children. Fifty-two healthy children (15-30 kg, 3-8 years of age) undergoing elective surgery with general anaesthesia and caudal block were studied and randomly allocated to two groups: caudal block or control. Following induction of anaesthesia, the first measurement was obtained in the supine position (baseline). All children were then turned to the left lateral position and patients in the caudal block group received a caudal block with bupivacaine. No intervention took place in the control group. After 15 nun in the supine position, the second assessment was performed. Functional residual capacity and parameters of ventilation distribution were calculated by a blinded reviewer. Functional residual capacity was similar at baseline in both groups. In the caudal block group, the capacity increased significantly (p < 0.0001) following caudal block, while in the control group, it remained unchanged. In both groups, parameters of ventilation distribution were consistent with the changes in functional residual capacity. Caudal block resulted in a significant increase in functional residual capacity and improvement in ventilation homogeneity in comparison with the control group. This indicates that caudal block might have a beneficial effect on gas exchange in anaesthetised, spontaneously breathing preschool-aged children with healthy lungs.

Is the French model giving way to a new 'Logic of Appropriateness'? Lessons from urban waste management

Processes of European integration and growing consumer scrutiny of public services have served to place the spotlight on the traditional French model of public/private interaction in the urban services domain. This article discusses recent debates within France of the institutionalised approach to local public/private partnership, and presents case study evidence from three urban agglomerations of a possible divergence from this approach. Drawing on the work of French academic, Dominique Lorrain, whose historical institutionalist accounts of the French model are perhaps the most comprehensive and best known, the article develops two hypotheses of institutional change, one from the historical institutionalist perspective of institutional stability and persistence, and the other from an explicitly sociological perspective, which emphasises the legitimating benefits of following appropriate rules of conduct. It argues that further studying the French model as an institution offers valuable empirical insight into processes of institutional change and persistence. © 2004 Taylor & Francis Ltd.

Incorporating Water Sensitive Urban Design (WSUD) practices into the planning context:the conceptual case for lot-scale developments

In recent decades, a number of sustainable strategies and polices have been created to protect and preserve our water environments from the impacts of growing communities. The Australian approach, Water Sensitive Urban Design (WSUD), defined as the integration of urban planning and design with the urban water cycle management, has made considerable advances on design guidelines since 2000. WSUD stormwater management systems (e.g. wetlands, bioretentions, porous pavement etc), also known as Best Management Practices (BMPs) or Low Impact Development (LID), are slowly gaining popularity across Australia, the USA and Europe. There have also been significant improvements in how to model the performance of the WSUD technologies (e.g. MUSIC software). However, the implementation issues of these WSUD practices are mainly related to ongoing institutional capacity. Some of the key problems are associated with a limited awareness of urban planners and designers; in general, they have very little knowledge of these systems and their benefits to the urban environments. At the same time, hydrological engineers should have a better understanding of building codes and master plans. The land use regulations are equally as important as the physical site conditions for determining opportunities and constraints for implementing WSUD techniques. There is a need for procedures that can make a better linkage between urban planners and WSUD engineering practices. Thus, this paper aims to present the development of a general framework for incorporating WSUD technologies into the site planning process. The study was applied to lot-scale in the Melbourne region, Australia. Results show the potential space available for fitting WSUD elements, according to building requirements and different types of housing densities. © 2011 WIT Press.

The combined impact of urban heat island, thermal bridge effect of buildings and future climate change on the potential overwintering of Phlebotomus species in a Central European metropolis

Leishmaniasis is one of the most important emerging vector-borne diseases in Western Eurasia. Although winter minimum temperatures limit the present geographical distribution of the vector Phlebotomus species, the heat island effect of the cities and the anthropogenic heat emission together may provide the appropriate environment for the overwintering of sand flies. We studied the climate tempering effect of thermal bridges and the heat island effect in Budapest, Hungary. Thermal imaging was used to measure the heat surplus of heat bridges. The winter heat island effect of the city was evaluated by numerical analysis of the measurements of the Aqua sensor of satellite Terra. We found that the surface temperature of thermal bridges can be at least 3-7 °C higher than the surrounding environment. The heat emission of thermal bridges and the urban heat island effect together can cause at least 10 °C higher minimum ambient temperature in winter nights than the minimum temperature of the peri-urban areas. This milder micro-climate of the built environment can enable the potential overwintering of some important European Phlebotomus species. The anthropogenic heat emission of big cities may explain the observed isolated northward populations of Phlebotomus ariasi in Paris and Phlebotomus neglectus in the agglomeration of Budapest.

Jerash: The landscape, urban space, and architecture

The peculiarities of Roman architecture, town planning, and landscape architecture are visible in many of the empire's remaining cities. However, evaluation of the landscapes; and analysis of the urban fabric, spatial compositions, and the concepts and characteristics of its open spaces are missing for Jerash (Gerasa in antiquity) in Jordan. Those missing elements will be discussed in this work, as an example of an urban arrangement that survived through different civilizations in history.^ To address the characteristics of the exterior spaces in Jerash, a study of the major concepts of planning in Classical Antiquity will be conducted, followed by a comparative analysis of the quality of space and architectural composition in Jerash. Through intensive investigation of data available for the area under study, the historical method used in this paper illustrates the uniqueness of the site's urban morphology and architectural disposition.^ An analysis will be performed to compare the design composition of the landscape, urban fabric, and open space of Jerash as a provincial Roman city with its existing excavated remains. Such an analysis will provide new information about the roles these factors and their relationships played in determining the design layout of the city. Information, such as the relationship between void and solid, space shaping, the ground and ceiling, the composition of city elements, the ancient landscapes, and the relationship between the land and architecture, will be acquired.^ A computer simulation for a portion of the city will be developed to enable researchers, students and citizens interested in Jordan's past to visualize more clearly what the city looked like in its prime. Such a simulation could result in the revival of the old city of Jerash and help promote its tourism. ^

Re-imagining Yerevan in the post-Soviet era: Urban symbolism and narratives of the nation in the landscape of Armenia's capital

The urban landscape of Yerevan has experienced tremendous changes since the collapse of the Soviet Union and Armenia’s independence in 1991. Domestic and foreign investments have poured into Yerevan’s building sector, converting many downtown neighborhoods into sleek modern districts that now cater to foreign investors, tourists, and the newly rich Armenian nationals. Large portions of the city’s green parks and other public spaces have been commercialized for private and exclusive use, creating zones that are accessible only to the affluent. In this dissertation I explore the rapidly transforming landscape of Yerevan and its connections to the development of contemporary Armenian national identity. This research was guided by principles of ethnographic inquiry, and I employed diverse methods, including document and archival research, structured and semi-structured interviews and content analysis of news media. I also used geographic information systems (GIS) and satellite images to represent and visualize the stark transformations of spaces in Yerevan. Informed by and contributing to three literatures—on the relationship between landscape and identity formation, on the construction of national identity, and on Soviet and post-Soviet cities—this dissertation investigates how messages about contemporary Armenian national identity are being expressed via the transforming landscape of Armenia’s national capital. In it I describe the ways in which abrupt transformations have resulted in the physical and symbolic eviction of residents, introducing fierce public debates about belonging and exclusion within the changing urban context. I demonstrate that the new additions to Yerevan’s landscape and the symbolic messages that they carry are hotly contested by many long-time residents, who struggle for inclusion of their opinions and interests in the process of re-imagining their national capital. This dissertation illustrates many of the trends that are apparent in post-Soviet and post-Socialist space, while at the same time exposing some unique characteristics of the Armenian case.

Aedes aegypti pharate first instar aseasonal quiescence cues anticipatory plasticity with implications for urban vector ecology and control

The eggs of the dengue fever vector Aedes aegypti possess the ability to undergo an extended quiescence period hosting a fully developed first instar larvae within its chorion. As a result of this life history stage, pharate larvae can withstand months of dormancy inside the egg where they depend on stored reserves of maternal origin. This adaptation known as pharate first instar quiescence, allows A. aegypti to cope with fluctuations in water availability. An examination of this fundamental adaptation has shown that there are trade-offs associated with it. ^ Aedes aegypti mosquitoes are frequently associated with urban habitats that may contain metal pollution. My research has demonstrated that the duration of this quiescence and the extent of nutritional depletion associated with it affects the physiology and survival of larvae that hatch in a suboptimal habitat; nutrient reserves decrease during pharate first instar quiescence and alter subsequent larval and adult fitness. The duration of quiescence compromises metal tolerance physiology and is coupled to a decrease in metallothionein mRNA levels. My findings also indicate that even low levels of environmentally relevant larval metal stress alter the parameters that determine vector capacity. ^ My research has also demonstrated that extended pharate first instar quiescence can elicit a plastic response resulting in an adult phenotype distinct from adults reared from short quiescence eggs. Extended pharate first instar quiescence affects the performance and reproductive fitness of the adult female mosquito as well as the nutritional status of its progeny via maternal effects in an adaptive manner, i.e., anticipatory phenotypic plasticity results as a consequence of the duration of pharate first instar quiescence and alternative phenotypes may exist for this mosquito with quiescence serving as a cue possibly signaling the environmental conditions that follow a dry period. M findings may explain, in part, A. aegypti's success as a vector and its geographic distribution and have implications for its vector capacity and control.^

Effects of increased urban and agricultural land use on the anthropogenic loading to southwest Florida estuaries

South Florida has been subject to considerable changes during the last 100 years. This study provides a detailed survey of the presence, concentration levels, and spatial distribution of organic and inorganic contaminants in sediment samples collected within the coastal environments of southwest Florida. It evaluates the potential contributions and effects of the urban and agricultural development to the pollution loading of the estuarine sediments. And it also provides information regarding chronology of contamination at impacted sites. Copper was found to be the most critical contaminant among the trace metals. 12% of the samples exceeded the Threshold Effects Level (TEL). None of organic contaminants measured exceeded the Probable Effects Level (PEL) criteria. Total PAHs concentrations exceeded the TEL criteria in 6% of the samples. The evaluation for the chronology of contamination showed a significant increase with time of every contaminant analyzed. Fluorescence spectroscopy proves to be a good method for fast screening PAHs.

Museum of urban development and headquarters for the planning/preservation department of the city of Miami Beach.

The objective of this research and thesis was to develop a program and project in the context of the Historic Art Deco District in Miami Beach. This project intended to analyze the chronological history of the urban development of the Art Deco District, its geographical, political and socio-cultural conditions as well as the evolution and different architectonic typologies of the area. In order to understand the issues involved in design in a historic context, this research addressed and analyzed several architectonic interventions within various historic places. This research concluded with the design of a public facility located at Ocean Drive, Miami Beach, consisting of a Museum of Urban Development and Headquarters for the Planning/Preservation Department of the City of Miami Beach. The project proposal and thesis, addresses architectonic and theoretical issues specific to design in an historic area.

Ink Under the Fingernails: Making Print in Nineteenth-Century Mexico City

This dissertation examines Mexico City’s material politics of print—the central actors engaged in making print, their activities and relationships, and the legal, business, and social dimensions of production—across the nineteenth century. Inside urban printshops, a socially diverse group of men ranging from manual laborers to educated editors collaborated to make the printed items that fueled political debates and partisan struggles in the new republic. By investigating how print was produced, regulated, and consumed, this dissertation argues that printers shaped some of the most pressing conflicts that marked Mexico’s first formative century: over freedom of expression, the role of religion in government, and the emergence of liberalism. Printers shaped debates not only because they issued texts that fueled elite politics but precisely because they operated at the nexus where new liberal guarantees like freedom of the press and intellectual property intersected with politics and patronage, the regulatory efforts of the emerging state, and the harsh realities of a post-colonial economy.

Historians of Mexico have typically approached print as a vehicle for texts written by elites, which they argue contributed to the development of a national public sphere or print culture in spite of low literacy levels. By shifting the focus to print’s production, my work instead reveals that a range of urban residents—from prominent printshop owners to government ministers to street vendors—produced, engaged, and deployed printed items in contests unfolding in the urban environment. As print increasingly functioned as a political weapon in the decades after independence, print production itself became an arena in struggles over the emerging contours of politics and state formation, even as printing technologies remained relatively unchanged over time.

This work examines previously unexplored archival documents, including official correspondence, legal cases, business transactions, and printshop labor records, to shed new light on Mexico City printers’ interactions with the emerging national government, and reveal the degree to which heated ideological debates emerged intertwined with the most basic concerns over the tangible practices of print. By delving into the rich social and cultural world of printing—described by intellectuals and workers alike in memoirs, fiction, caricatures and periodicals— it also considers how printers’ particular status straddling elite and working worlds led them to challenge boundaries drawn by elites that separated manual and intellectual labors. Finally, this study engages the full range of printed documents made in Mexico City printshops not just as texts but also as objects with particular visual and material qualities whose uses and meanings were shaped not only by emergent republicanism but also by powerful colonial legacies that generated ambivalent attitudes towards print’s transformative power.

Three-dimensional outcomes of twin-block appliance treatment and the influence of the postured wax bite

Aims 1 To identify the 3D soft tissue volumetric and linear landmark changes following treatment with the Twin-Block Appliance TBA. 2 To estimate the TBA treatment outcome on the soft tissue facial profile volumetric and linear landmark changes from the Postured Wax Bite (PWB). 3 To identify if there is any association between certain soft tissue landmark variables and successful treatment outcome of the TBA as measured by the reduction in overjet. 4 To assess the effects of TBA treatment on facial expressions. Materials and Methods Forty-seven Caucasian subjects with Class II division 1 were recruited. 3D images captured of each subject, pre-treatment (T1), with the PWB (T2) and at the end of treatment (T3). Soft tissue volumetric and linear changes as well as the correlation between facial parameters and successful treatment were calculated. Results The mean soft tissue volumetric change from T1 to T3 was 22.24 ± 16.73 cm³. Soft tissue profile linear changes from T1-T3 for lower facial landmarks were 4-5 mm. From T1-T3, the mean soft tissue volumetric change of the total sample was 60% of the change produced by the PWB (T1 to T2). Correlations were weak for all 3D facial parameters and successful overjet reduction. Facial expression changes were only significant for the lower landmarks. Conclusions 1 TBA treatment, in growing subjects, increased the lower facial soft tissue volume and caused forward movement of the lower soft tissue facial profile landmarks.2 The PWB can be used to estimate the treatment outcome of the TBA on soft tissue profile changes.3 No association was found between soft tissue landmark variables and successful overjet reduction.4 TBA treatment had no effect on the upper facial landmarks for each facial expression but it changed the lower facial expressions significantly except for maximal smile in males.

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.

AUTO-RUINS. Thinks about automobile into the contemporary landscape

The article analyses the evolution of the representation of the automobile inserted in the natural and urban environment in the Contemporary Art, from the appearance of the first cars in the beginning of the 20th century until the present day. The text compares the diverse attitudes and analysis of some representative artists who have used the image of the machine in general and the car in particular in their aesthetic discourse, using as a conductive thread the metaphor of the life cycle (birth, growth, feeding, reproduction and death). It deals with the discovery, the development and the coexistence between human and the automobile and its interpretation as a basic element of the artistic work. The text connects the image of the automobile located in the contemporary industrial landscape utilizing the artist references who have integrated the car in their work inside the natural or artificial environment characteristic of each moment. At the same time, the article goes deeply into the relationship of romantic ruin and natural landscape and the evolution of the industrial and architectural modern environment, through the work of the artists who has used the car as an inhabitant of the landscape.

Primitivism, Regionalism, and the Vernacular in Le Corbusier's middle years, 1929-1945

Thesis (Master's)--University of Washington, 2016-06