Nanoporous solid acid and base catalysts for sustainable biofuels production

Dwindling fossil fuel reserves, and growing concerns over CO2 emissions and associated climate change, are driving the quest for renewable feedstocks to provide alternative, sustainable fuel sources. Catalysis has a rich history of facilitating energy efficient, selective molecular transformations, and in a post-petroleum era will play a pivotal role in overcoming the scientific and engineering barriers to economically viable, and sustainable, biofuels derived from renewable resources. The production of second generation biofuels, derived from biomass sourced from inedible crop components, e.g. agricultural or forestry waste, or alternative non-food crops such as Switchgrass or Jatropha Curcas that require minimal cultivation, necessitate new heterogeneous catalysts and processes to transform these polar and viscous feedstocks [1]. Here we show how advances in the rational design of nanoporous solid acids and bases, and their utilisation in novel continuous reactors, can deliver superior performance in the energy-efficient esterification and transesterification of bio-oil components into biodiesel [2-4]. Notes: [1] K. Wilson, A.F. Lee, Cat. Sci. Tech. 2012 ,2, 884. [2] J. Dhainaut, J.-P. Dacquin, A. F. Lee, K. Wilson, Green Chem. 2010 , 12, 296. [3] C. Pirez, J.-M. Caderon, J.-P. Dacquin, A.F. Lee, K. Wilson, ACS Catal. 2012 , 2, 1607. [4] J.J. Woodford, J.-P. Dacquin, K. Wilson, A.F. Lee, Energy Environ. Sci. 2012 , 5, 6145.

Synthesis and characterization of silica-supported L-Lysine-based dendritic branches

Two series of novel modified silicas have been prepared in which individual dendritic branches have been attached to aminopropylsilica using standard peptide coupling methodology. The dendritic branches are composed of enantiomerically pure l-lysine building blocks, and hence, the modified silicas have the potential to act as chiral stationary phases in chromatography. In one series of modified silicas, the surface of the dendritic branch consists of Boc carbamate groups, whereas the other has benzoyl amide surface groups. Different coupling reagents have been investigated in order to maximize the loading onto the solid phase. The new supported dendritic materials have been fully characterized with properties of the bulk material determined by elemental analysis, 13C NMR, and IR spectroscopy, whereas XPS provides important information about the surface of the modified silica exposed to the incident X-rays, the key region in which potential chromatographic performance of these materials will take place. Although the bulk analyses indicate that loading of the dendritic branch onto silica decreases with increasing dendritic generation (and consequently steric bulk), XPS indicates that the optimum surface coverage is actually obtained at the second generation of dendritic growth.

Boundary maintenance in Qatar: Interpretation of domination, segregation and subordination

This study explores the interaction of expatriates in Qatar and their perception of their subordination. The study design included participant observation in an all female University and University housing as well as interviews with Qatari government agencies and ministries, expatriate embassies and expatriates. Semi-structured interviews were conducted across seven expatriate groups: domestic workers, unskilled laborers, semiskilled, professionals, housewives, second-generation expatriates with host country other than Qatar, second-generation expatriates with host country Qatar, and Gulf Cooperation Council citizens. Forty-two subjects completed the interview schedule while 87 interviews were incomplete. ^ Physical control of expatriates occurs through the Gulf practice of sponsorship (The Kafeel System), and local cultural and Islamic related controls intertwined with the Arab Code of honor. Interviews and observations revealed rankings of Arabs and foreigners which emphasize Qatari superiority such as tribal identity, moral ranking of female groups by dress, legal protection and power, sexual consideration and desexualization and salaries and job opportunities based on nationality and ethnicity. Individuals who desire to transcend boundaries into the Qatari realm through citizenship or marriage view Qataris as possessing the “image of the unlimited good” and have acquired Qatari social and cultural capital. Members from all expatriate groups engaged in various forms of resistance to labor and gender domination which ranged from forms of “exit,” expressing a hidden transcript in the privacy of their own group, disguised resistance in public, and occasionally, direct confrontation with the Qatari. Although the legal arena created the appearance that worker's needs were being addressed, laborers engaged in forms of “exit” to escape their oppression. Omani students in the hostel disguised their resistance by spreading gossip, nick-naming homosexual Qatari students at the University, acting out a skit depicting their exclusion from Qatari privilege, spreading rumors of impending freedom, and singing songs of despair in the courtyard. Other sites of resistance were expatriate embassies, the road, the newspaper and technology. This study emphasizes that blaming oppression of the expatriate worker on globalization is a simplistic view of oppression in the Gulf, and ignores complex issues within Qatari society and other Gulf States. Sponsorship, servitude, and gender segregation intersect in Qatar to create a system of segregation and domination of expatriates. ^

Therapeutic azulenyl nitrone antioxidants

The reactions of nitrones with free radicals have been widely studied both in vitro and in vivo. In comparison to classical chain-breaking phenolic antioxidants (such as Vitamin E and butylated hydroxytoluene [BHT]), conventional phenyl-substituted nitrones have much higher oxidation potentials. Azulenyl-substituted nitrones have lower oxidation potentials than conventional nitrones and react efficiently with free radicals in vitro and in vivo. The design and synthesis of novel azulenyl nitrones with yet lower oxidation potentials, prepared from commercially available guaiazulene, has produced several 1,2-trans -bis-azulenyl ethene compounds with enhanced antioxidant activity. A convenient 1H NMR-based assay for assessing the potency of chain-breaking antioxidants has shown these novel nitrones to be more than 300 times more potent in inhibiting the free radical-mediated aerobic peroxidation of cumene than α-phenyl-N-tert-butyl nitrone (PBN) and the experimental stroke drug NXY-059. The low oxidation potential of these novel nitrones and the stability of the corresponding radical cation have been implicated in the explanation of the increased antioxidant potency of these second generation azulenyl nitrones. Based on the results of these in vitro studies, the first of these novel compounds, stilbazulenyl nitrone (STAZN), was investigated in animal models of disease known to involve free radical-mediated pathology. In view of STAZN's marked lipophilicity and anticipated blood brain barrier permeability, neurodegenerative conditions were investigated. All animal experiments were performed at the University of Miami by members of the Ginsberg research group. STAZN was neuroprotective in traumatic brain injury in rats. It also provided exceptional neuroprotection in an animal model of stroke. The concentration of STAZN required for neuroprotection was 300–600 times less than doses of PBN or NXY-059 required for similar effect. Thus, the benefits of greater antioxidant potency sought by lowering the oxidation potential of nitrones appear to have been reaped both in vitro and in vivo. In spite of the challenges and difficulties in understanding free radical-mediated pathology, this work establishes that considerations such as redox potential and lipophilicity can provide a very fruitful rationale for the design of therapeutic azulenyl nitrone antioxidants. ^

Synthetic studies of azulenyl and pseudoazulenyl nitrones

Free radicals have been implicated in various pathological conditions such as, stroke, aging and ischemic heart disease (IHD), as well as neurodegenerative diseases like Alzheimer’s, Parkinson’s, and Huntington’s disease. The role of antioxidants in protection from the harmful effects of free radicals has long been recognized. Trapping extremely reactive free radicals and eliminating them from circulation has been shown to be effective in animal models. Nitrone-based free radical traps have been extensively explored in biological systems. Examples include nitrones such as PBN, NXY-059, MDL-101,002, DMPO and EMPO. However, these nitrones have extremely high oxidation potentials as compared to natural antioxidants such as Vitamin E (α-tocopherol), and glutathione. Becker et al. (1995) synthesized novel azulenyl nitrones, which were shown to have oxidation potentials much lower than that of any of the previously reported nitrone based spin traps. Another azulenyl nitrone derivative, stilbazulenyl nitrone (STAZN), was shown to have an even lower oxidation potential within the range of natural antioxidants. STAZN, a second generation free radical trap, was found to be markedly superior than the two most studied nitrones, PBN and NXY-059, in animal models of cerebral ischemia and in an in vitro assay of lipid peroxidation. In this study, a third generation azulenyl nitrone was synthesized with an electron donating group on the previously synthesized STAZN derivative with the aim to lower the oxidation potential even more. Pseudoazulenes, because of the presence of an annular heteroatom, have been reported to possess even lower oxidation potential than that of the azulenyl counterpart. Therefore, pseudoazulenyl nitrones were synthesized for the first time by extracting and elaborating valtrate from the roots of Centranthus ruber (Red valerian or Jupiter’s beard). Several pseudoazulenyl nitrones were synthesized by using a facile experimental protocol. The physical and biological properties of these pseudoazulenyl nitrones can be easily modified by simply changing the substituent on the heteroatom. Cyclic voltammetry experiments have shown that these pseudoazulenyl nitrones do indeed have low oxidation potentials. The oxidation potential of these nitrones was lowered even more by preparing derivatives bearing an electron donating group at the 3-position of the five membered ring of the pseudoazulenyl nitrone.

The experiences of Cuban American women attending a Hispanic serving institution and the influences on identity development

The purpose of this study was to gain an understanding and gather insight into the experiences of Cuban American women attending a 4-year, public, Hispanic Serving Institution and how those experiences influenced their identity development. This was accomplished by conducting in-depth interviews and focus groups with 12 self-identified Cuban American women who were classified as sophomores, juniors, seniors, or graduate students. All of the participants had attended Florida International University for at least 1 year. The women had varying degrees of on and off campus academic and campus involvement activities. Participants were asked about six topics: (a) family, (b) cultural influences, (c) gender, (d) ethical and moral development, (e) education, and (f) ethnic identity. Based on the coding of the data provided by the participants, several interconnected themes emerged including the importance of family, familial support, cultural pride, expected gender roles, core values, decision making, biculturalism, and the value of attending a Hispanic Serving Institution. These themes were found to be all related to the identity development of the participants. It was found that looking at identity through a multidimensional lens is essential. Looking at personal growth and development through anthropological, sociological, and psychosocial lenses gave greater insight to a population of students who have been largely underrepresented in the literature. The findings of this case study are that culture is contextual and identity development is complex for first and second generation Cuban American women attending a Hispanic Serving Institution in a majority minority city. It was found that several factors, including the importance of family and gender roles, were not found to be more important than one another; rather they supported each other in regards to the participants' identity development. The notion of biculturalism as it has been presented in the literature was challenged in this study as it was found that the participants' experiences living and attending a school in a majority minority city presented a new way of understanding what it might mean to be bicultural. For professionals in the field, the findings of this study may lead to a broader understanding of nuances within the Hispanic community and a better understanding of the distinctiveness of what it means to be a Cuban American woman.

The relationship of immigrant status to perceptions of reading and reading literacy among young Black students: A test of the Cultural -Ecological Theory of School Performance

This study tests Ogbu and Simons' Cultural-Ecological Theory of School Performance using data from the Progress in International Reading Literacy Study of 2001 (PIRLS), a large-scale international survey and reading assessment involving fourth grade students from 35 countries, including the United States. This theory argues that Black immigrant students outperform their non-immigrant counterparts, academically, and that achievement differences are attributed to stronger educational commitment in Black immigrant families. Four hypotheses are formulated to test this theory: Black immigrant students have (a) more receptive attitudes toward reading; (b) a more positive reading self-concept; and (c) a higher level of reading literacy. Furthermore, (d) the relationship of immigrant status to reading perceptions and literacy persists after including selected predictors. These hypotheses are tested separately for girls and boys, while also examining immigrant students' generational status (i.e., foreign-born or second-generation). ^ PIRLS data from a subset of Black students (N=525) in the larger U.S. sample of 3,763 are analyzed to test the hypotheses, using analysis of variance, correlation and multiple regression techniques. Findings reveal that hypotheses a and b are not confirmed (contradicting the Cultural-Ecological Theory) and c and d are partially supported (lending partial support to the theory). Specifically, immigrant and non-immigrant students did not differ in attitudes toward reading or reading self-concept; second-generation immigrant boys outperformed both non-immigrant and foreign-born immigrant boys in reading literacy, but no differences were found among girls; and, while being second-generation immigrant had a relatively stronger relationship to reading literacy for boys, among girls, selected socio-cultural predictors, number of books in the home and length of U.S. residence, had relatively stronger relationship to reading self-concept than did immigrant status. This study, therefore, indicates that future research employing the Cultural-Ecological Theory should: (a) take gender and generational status into account (b) identify additional socio-cultural predictors of Black children's academic perceptions and performance; and (c) continue to build on this body of evidence-based knowledge to better inform educational policy and school personnel in addressing needs of all children. ^

The impact of migration and intergenerational changes on the Cuban family in the United States

This study examines changes in the Cuban family in the United States produced by time, migration, and the rise of new generations. The thesis will use a data set extracted from the 5% Public Use Microdata Series (PUMS) of the U.S. Decennial Census of Population for the years 1970, 1980 and 1990. Contingency table analysis and comparison of means were used to examine various family-related variables. The analysis points to changes in the traditional Cuban family towards less traditional family arrangements. The multigenerational feature of the Cuban household has diminished as the elderly have become independent and are more likely to be living on their own. Although female labor participation remains high, the occupational patterns of the first generation of Cuban women have diversified and a new trend has emerged for the second generation. The second generation of Cuban women demonstrates a strong inclination for white-collar occupations. Fertility rates remain low.

Sociophonetic history of Newfoundland English in Happy Valley-Goose Bay, Labrador

In this paper, I report on the variety of English spoken in the relatively new community of Happy Valley-Goose Bay, Labrador. The efects of dialect contact and the process of dialect levelling (Trudgill 1986; Britain 1997, Kerswill and Williams 2000; Kerswill 2002) are observed by examining the development of several vowels in the Happy Valley- Goose Bay vowel system. In this community the migrant generation showed evidence of mixing. The frst generation showed the most evidence of levelling along with the emergence of new distinctions. The second generation showed some evidence of levelling, the emergence of new distinctions, and in some cases a return to patterns present in the migrant generation. These results indicate that diferent vowels within a dialect can move through the stages of dialect contact at diferent rates due to the multitude of infuences on the process of dialect contact.

WEBJORNALISMO COLABORATIVO - A PRESENÇA DOS USUÁRIOS NO CONTEÚDO INFORMATIVO DO PORTAL R7

Este estudo procura verificar como ocorre a colaboração dos usuários no conteúdo informativo do Portal R7, a partir da nova configuração da internet, a web 2.0, criada em 2004. O termo web 2.0 surgiu para qualificar uma segunda geração de comunidades e serviços, em um ambiente de interação e participação que engloba diversas linguagens. Com o crescimento da adesão à tecnologia digital, algumas barreiras que limitavam a colaboração nos conteúdos informativos foram superadas e o ambiente comunicacional tornou-se um espaço de intercâmbio para experiências e práticas do cotidiano. Nesse cenário, os internautas passam a ter uma relação mais aproximativa nos processos midiáticos presentes no suporte digital, no qual o cidadão pode se expressar, ter maior visibilidade e se relacionar a partir do momento em que ele produz, publica e compartilha qualquer tipo de conteúdo, seja de caráter informativo ou de entretenimento. A revisão bibliográfica abrangeu autores como Ciro Marcondes Filho, José Marques de Melo, Nelson Traquina, Alex Primo, Ana Brambilla, Marcelo Träsel, Raquel Recuero, Polyana Ferrari, Squirra, entre outros. O método de investigação utilizado é o qualitativo, por meio de uma pesquisa exploratória descritiva, do tipo estudo de caso. Os instrumentos para a investigação foram a observação direta assistemática e a entrevista semiestruturada (ou semiaberta). O principal resultado obtido é que o webjornalismo colaborativo no Portal R7 é prioritariamente induzido pelas redes sociais, especialmente o Facebook e o Twitter, inspirado no “call for action”, como estratégia para chamar à colaboração. As práticas jornalísticas estão intrinsicamente dependentes da ação do usuário, sendo que o jornalista agrega às práticas de checagem uma nova etapa, a de relacionamento com o usuário do Portal, para agregar e fidelizar a audiência, valorizando a colaboração em todas as etapas de produção.

Targeted sequencing for high-resolution evolutionary analyses following genome duplication in salmonid fish : Proof of concept for key components of the insulin-like growth factor axis

Acknowledgements This study was funded by a Natural Environment Research Council grant (NERC, project code: NBAF704). FML is funded by a NERC Doctoral Training Grant (Project Reference: NE/L50175X/1). RLS was an undergraduate student at the University of Aberdeen and benefitted from financial support from the School of Biological Sciences. DJM is indebted to Dr. Steven Weiss (University of Graz, Austria), Dr. Takashi Yada (National Research Institute of Fisheries Science, Japan), Dr. Robert Devlin (Fisheries and Oceans Canada, Canada), Prof. Samuel Martin (University of Aberdeen, UK), Mr. Neil Lincoln (Environment Agency, UK) and Prof. Colin Adams/Mr. Stuart Wilson (University of Glasgow, UK) for providing salmonid material or assisting with its sampling. We are grateful to staff at the Centre for Genomics Research (University of Liverpool, UK) (i.e. NERC Biomolecular Analysis Facility – Liverpool; NBAF-Liverpool) for performing sequence capture/Illumina sequencing and providing us with details on associated methods that were incorporated into the manuscript. Finally, we are grateful to the organizers of the Society of Experimental Biology Satellite meeting 'Genome-powered perspectives in integrative physiology and evolutionary biology' (held in Prague, July 2015) for inviting us to contribute to this special edition of Marine Genomics and hosting a really stimulating meeting.

The Didache and Traditioned Innovation: Shaping Christian Community in the First Century and the Twenty-First Century

Church leaders, both lay and clergy, shape Christian community. Among their central tasks are: building communal identity, nurturing Christian practices, and developing faithful structures. When it comes to understanding the approach of the earliest Christian communities to these tasks, the Didache might well be the most important text most twenty-first century church leaders have never read. The Didache innovated on tradition, shaping the second generation of Christians to meet the crises and challenges of a changing world.

Most likely composed in the second half of the first century, the Didache served as a training manual for gentile converts to Christianity, preparing them for life in Christian community. This brief document, roughly one third the length of Mark’s gospel, developed within early Jewish-Christian communities. It soon found wide usage throughout the Mediterranean region, and its influence endured throughout the patristic and into the medieval period.

The Didache outlines emerging Christian practices that were rooted in both Jewish tradition and early Jesus material, yet were reaching forward in innovative ways. The Didache adopts historical teachings and practices and then adapts them for an evolving context. In this respect, the writers of the Didache, as well as the community shaped by its message, exemplify the pattern of thinking described by Greg Jones as “traditioned innovation.”

The Didache invites reflection on the shape and content of Christian community and Christian leadership in the twenty-first century. As churches and church leaders engage a rapidly changing world, the Didache is an unlikely and yet important conversation partner from two millennia ago. A quick read through its pages – a task accomplished in less than half an hour – brings the reader face to face with a brand of Christianity both very familiar and strikingly dissimilar to modern Christianity. Such dissonance challenges current assumptions about the church and creates a space in which to re-imagine our situation in light of this ancient Christian tradition. The Didache provides a window through which we might re-examine current conceptualizations of Christian life, liturgy, and leadership.

This thesis begins with an exploration of the form and function of the Didache and an examination of a number of important background issues for the informed study of the Didache. The central chapters of this thesis exegete and explore select passages in each of the three primary sections of the Didache – the Two Ways (Didache 1-6), the liturgical section (Didache 7-10), and the church order (Didache 11-15). In each instance, the composers of the Didache reach back into a cherished and life-giving aspect of the community’s heritage and shape it anew into a fresh and faithful approach to living the Christian life in a drastically different context.

The thesis concludes with three suggestions of how the Didache may provide a resource for the way the Church in the present thinks about training disciples, shaping community, and developing leadership structures. These conversation starters offer beginning points for a richer, fuller discussion of traditioned innovation in our current church context. The Didache provides a source of wisdom from our spiritual forebears that modern Christian leaders would do well not to ignore. With a look through the first century window of the Didache, twenty-first century Christians can discover fresh insights for shaping Christian community in the present.

Development of miniaturized antennas and adaptive tuning solutions for body sensor network applications

Wireless Sensor Networks (WSNs) are currently having a revolutionary impact in rapidly emerging wearable applications such as health and fitness monitoring amongst many others. These types of Body Sensor Network (BSN) applications require highly integrated wireless sensor devices for use in a wearable configuration, to monitor various physiological parameters of the user. These new requirements are currently posing significant design challenges from an antenna perspective. This work addresses several design challenges relating to antenna design for these types of applications. In this thesis, a review of current antenna solutions for WSN applications is first presented, investigating both commercial and academic solutions. Key design challenges are then identified relating to antenna size and performance. A detailed investigation of the effects of the human body on antenna impedance characteristics is then presented. A first-generation antenna tuning system is then developed. This system enables the antenna impedance to be tuned adaptively in the presence of the human body. Three new antenna designs are also presented. A compact, low-cost 433 MHz antenna design is first reported and the effects of the human body on the impedance of the antenna are investigated. A tunable version of this antenna is then developed, using a higher performance, second-generation tuner that is integrated within the antenna element itself, enabling autonomous tuning in the presence of the human body. Finally, a compact sized, dual-band antenna is reported that covers both the 433 MHz and 2.45 GHz bands to provide improved quality of service (QoS) in WSN applications. To date, state-of-the-art WSN devices are relatively simple in design with limited antenna options available, especially for the lower UHF bands. In addition, current devices have no capability to deal with changing antenna environments such as in wearable BSN applications. This thesis presents several contributions that advance the state-of-the-art in this area, relating to the design of miniaturized WSN antennas and the development of antenna tuning solutions for BSN applications.

Synthetic Studies of Azulenyl and Pseudoazulenyl Nitrones

Free radicals have been implicated in various pathological conditions such as, stroke, aging and ischemic heart disease (IHD), as well as neurodegenerative diseases like Alzheimer’s, Parkinson’s, and Huntington’s disease. The role of antioxidants in protection from the harmful effects of free radicals has long been recognized. Trapping extremely reactive free radicals and eliminating them from circulation has been shown to be effective in animal models. Nitrone-based free radical traps have been extensively explored in biological systems. Examples include nitrones such as PBN, NXY-059, MDL-101,002, DMPO and EMPO. However, these nitrones have extremely high oxidation potentials as compared to natural antioxidants such as Vitamin E (á-tocopherol), and glutathione. Becker et al. (1995) synthesized novel azulenyl nitrones, which were shown to have oxidation potentials much lower than that of any of the previously reported nitrone based spin traps. Another azulenyl nitrone derivative, stilbazulenyl nitrone (STAZN), was shown to have an even lower oxidation potential within the range of natural antioxidants. STAZN, a second generation free radical trap, was found to be markedly superior than the two most studied nitrones, PBN and NXY-059, in animal models of cerebral ischemia and in an in vitro assay of lipid peroxidation. In this study, a third generation azulenyl nitrone was synthesized with an electron donating group on the previously synthesized STAZN derivative with the aim to lower the oxidation potential even more. Pseudoazulenes, because of the presence of an annular heteroatom, have been reported to possess even lower oxidation potential than that of the azulenyl counterpart. Therefore, pseudoazulenyl nitrones were synthesized for the first time by extracting and elaborating valtrate from the roots of Centranthus ruber (Red valerian or Jupiter’s beard). Several pseudoazulenyl nitrones were synthesized by using a facile experimental protocol. The physical and biological properties of these pseudoazulenyl nitrones can be easily modified by simply changing the substituent on the heteroatom. Cyclic voltammetry experiments have shown that these pseudoazulenyl nitrones do indeed have low oxidation potentials. The oxidation potential of these nitrones was lowered even more by preparing derivatives bearing an electron donating group at the 3-position of the five membered ring of the pseudoazulenyl nitrone.

Memorias en voz baja : Transmisión oral intergeneracional: de Os libros arden mal a As voces baixas

Este trabajo analiza la forma en que se desarrolla un traspaso de la experiencia del pasado traumático en dos textos de Manuel Rivas en los que adquiere gran protagonismo el discurso oral. La Guerra Civil española y sus consecuencias son incorporadas a la narrativa de Os libros arden mal y As voces baixas con especial énfasis en las generaciones que no vivieron esos años. Las convergencias entre oralidad y escritura resultan un terreno fértil para considerar la inclusión de voces largamente postergadas debido a silencios impuestos y a la represión de verdades que tardaron en visibilizarse.