Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C=O over C=C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C=O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes.

Development and verification of control and protection strategies in hybrid AC/DC power systems for smart grid applications

Modern power networks incorporate communications and information technology infrastructure into the electrical power system to create a smart grid in terms of control and operation. The smart grid enables real-time communication and control between consumers and utility companies allowing suppliers to optimize energy usage based on price preference and system technical issues. The smart grid design aims to provide overall power system monitoring, create protection and control strategies to maintain system performance, stability and security. This dissertation contributed to the development of a unique and novel smart grid test-bed laboratory with integrated monitoring, protection and control systems. This test-bed was used as a platform to test the smart grid operational ideas developed here. The implementation of this system in the real-time software creates an environment for studying, implementing and verifying novel control and protection schemes developed in this dissertation. Phasor measurement techniques were developed using the available Data Acquisition (DAQ) devices in order to monitor all points in the power system in real time. This provides a practical view of system parameter changes, system abnormal conditions and its stability and security information system. These developments provide valuable measurements for technical power system operators in the energy control centers. Phasor Measurement technology is an excellent solution for improving system planning, operation and energy trading in addition to enabling advanced applications in Wide Area Monitoring, Protection and Control (WAMPAC). Moreover, a virtual protection system was developed and implemented in the smart grid laboratory with integrated functionality for wide area applications. Experiments and procedures were developed in the system in order to detect the system abnormal conditions and apply proper remedies to heal the system. A design for DC microgrid was developed to integrate it to the AC system with appropriate control capability. This system represents realistic hybrid AC/DC microgrids connectivity to the AC side to study the use of such architecture in system operation to help remedy system abnormal conditions. In addition, this dissertation explored the challenges and feasibility of the implementation of real-time system analysis features in order to monitor the system security and stability measures. These indices are measured experimentally during the operation of the developed hybrid AC/DC microgrids. Furthermore, a real-time optimal power flow system was implemented to optimally manage the power sharing between AC generators and DC side resources. A study relating to real-time energy management algorithm in hybrid microgrids was performed to evaluate the effects of using energy storage resources and their use in mitigating heavy load impacts on system stability and operational security.

Overweight/Obesity and HIV Disease Progression in HIV+ Adults in Botswana

Studies indicate that overweight and obesity protect against HIV-disease progression in antiretroviral therapy (ART)-naïve patients. We examined retrospectively the relationship of overweight/obesity with HIV-disease progression in ART-naïve HIV+ adults in Botswana in a case-control study with 18-month follow-up, which included 217 participants, 139 with BMI 18.0-24.9 kg/m2 and 78 with BMI ≥25 kg/m2. Archived plasma samples were used to determine inflammatory markers: leptin and bacterial endotoxin lipopolysaccharide (LPS), and genotype single nucleotide polymorphisms (SNPs) of the Fat Mass and Obesity Associated Gene (FTO). At baseline, BMI was inversely associated with risk for AIDS-defining conditions (HR=0.218; 95%CI=0.068, 0.701, P=0.011), and higher fat mass was associated with reduced risk of the combined outcome of CD4+cell count ≤250/µL and AIDS-defining conditions, whichever occurred earlier (HR=0.918; 95%CI=0.847, 0.994, P=0.036) over 18 months, adjusting for age, gender, marriage, children, and baseline CD4+cell count and HIV-viral load. FTO-SNP rs17817449 was associated with BMI (OR=1.082; 95%CI=1.001, 1.169; P=0.047). Fat mass was associated with the risk alleles of rs1121980 (OR=1.065; 95%CI=1.009, 1.125, P=0.021), rs8050136 (OR=1.078; 95%CI=1.021, 1.140; P=0.007), and rs17817449 (OR=1.086; 95%CI=1.031, 1.145; P=0.002), controlling for age, gender, tribe, total energy intake, and activity. There were no associations of SNPs with markers of disease progression. Leptin levels were positively associated with BMI (β=1.764; 95%CI=0.788, 2.739; P=0.022) and fat mass (β=0.112; 95%CI=0.090, 0.135; P<0.001), but inversely with viral load (β=-0.305; 95%CI=-0.579, -.031; P=0.030). LPS levels were inversely associated with BMI (OR=0.790, 95%CI=0.630, 0.990; P=0.041), and fat mass (OR=0.852, 95%CI=0.757, 0.958; P=0.007) and directly with viral load (OR=2.608, 95%CI=1.111, 6.124; P=0.028), adjusting for age, gender, smoking and %fat mass. In this cohort, overweight/obesity predicted slower HIV-disease progression. Obesity may confer an advantage in maintaining fat stores to support the overactive immune system. FTO-SNPs may contribute to the variation in fat mass; however, they were not associated with HIV-disease progression. Our findings suggest that the obesity paradox may be explained by the association of increased LPS with lower BMI and higher viral load; while viral load decreased with increasing leptin levels. Studies in African populations are needed to clarify whether genetic variation and inflammation mediate the obesity paradox in HIV-disease progression.

Love comes in at the eye

LOVE COMES IN AT THE EYE relates the story of Marshall Craig, a Midwesterner transplanted to South Florida who turns 35 in the course of the book. Marshall is an assistant curator for a Miami art museum, a man who has been obsessed with--as he calls it--a greed for seeing from a young age. His fascination with the surface of appearance of things is exacerbated by his precocious studies in art and its histories. Marshall views himself as marked by his red hair and freckled skin, as someone whose chances of attracting a partner into a meaningful relationship have been diminished by his looks. He is colored by his image of himself as unattractive and most importantly, convinced that his romantic life would be more successful, more vibrant, if he'd been graced with the face and figure of, say, a Velazquez. When Marshall meets a Cuban-born man from Atlanta, he is transfixed by the conviction that this is the man the universe has selected for him. The thrust of the story goes beyond boy-meets/loses/gets-boy to an exploration of said boy coming to terms with his definition of self. In a pivotal span of six months, the book explores Marshall's obsessions with seeing and how they define his vision of reality, the emphasis placed on beauty in gay culture, the tentative beginnings of a relationship as it takes root and grows, and finally, the inexplicable, magical forces that direct our romantic destinies.

Reimagining the Baroque in Italian Modernism. From the fin-de-siècle to Lucio Fontana

While Italian art of the twentieth century is usually associated with either the avant-garde practices of Futurism or the classicism of Fascist visual culture, the Italian modernists' complex engagement with concepts of the ‘Baroque’ has yet to be explored. Through an extensive analysis of paintings, sculptures, publications, collecting practices, and exhibitions, my dissertation addresses this lacuna by investigating how the Baroque was discursively constructed and visually represented in Italian modernist artistic and cultural debates between 1880 and 1945. I study how artists and critics such as Umberto Boccioni, Giorgio De Chirico, Adolfo Wildt, Lucio Fontana, and Roberto Longhi championed or disparaged the Baroque in the context of heated debates over the import of Italy’s rich cultural heritage, its status in modern Europe, and the potential role of avant-garde art as a catalyst for national regeneration. In contrast to previous scholars I argue that the development of modern art in Italy was actively shaped by cultural perceptions about the Baroque. My dissertation therefore sheds new light on the role of style in the cultural politics of Italy, which in turn will transform our understanding of visual culture in modern Italy, and of twentieth-century representations of the Baroque in art, literature, and aesthetics.

(Figure 2) Stratigraphic distribution of Schizosphaerella in DSDP Hole 79-547B

The Jurassic (hemi)pelagic continental margin deposits drilled at Hole 547B, off the Moroccan coast, reveal striking Tethyan affinity. Analogies concern not only types and gross vertical evolution of facies, but also composition and textures of the fine sediment and the pattern of diagenetic alteration. In this context, the occurrence of the nanno-organism Schizosphaerella Deflandre and Dangeard (sometimes as a conspicuous portion of the fine-grained carbonate fraction) is of particular interest. Schizosphaerella, an incertae sedis taxon, has been widely recorded as a sediment contributor from Tethyan Jurassic deeper-water carbonate facies exposed on land. Because of its extremely long range (Hettangian to early Kimmeridgian), the genus Schizosphaerella (two species currently described, S. punctulata Deflandre and Dangeard and S. astrea Moshkovitz) is obviously not of great biostratigraphic interest. However, it is of interest in sedimentology and petrology. Specifically, Schizosphaerella was often the only component of the initial fine-grained fraction of a sediment that was able to resist diagenetic obliteration. However, alteration of the original skeletal structure did occur to various degrees. Crystal habit and mineralogy of the fundamental skeletal elements, as well as their mode of mutual arrangement in the test wall with the implied high initial porosity of the skeleton (60-70%), appear to be responsible for this outstanding resistance. Moreover, the ability to concentrate within and, in the case of the species S. punctulata, around the skeleton, large amounts of diagenetic calcite also contributed to the resistance. In both species of Schizosphaerella, occlusion of the original skeletal void space during diagenesis appears to have proceeded in an analogous manner, with an initial slight uniform syntaxial enlargement of the basic lamellar skeletal crystallites followed, upon mutual impingement, by uneven accretion of overgrowth cement in the remaining skeletal voids. However, distinctive fabrics are evident according to the different primary test wall architecture. In S. punctulata, intraskeletal cementation is usually followed by the growth of a radially structured crust of bladed to fibrous calcite around the valves. These crusts are interpreted as a product of aggrading neomorphism, associated with mineralogic stabilization of the original, presumably polyphase, sediment. Data from Hole 547B, along with inferences, drawn from the fabric relationships, suggest that the crusts formed and (inferentially) mineralogic stabilization occurred at a relatively early time in the diagenetic history in the shallow burial realm. An enhanced rate of lithification at relatively shallow burial depths and thus the chance for neomorphism to significantly influence the textural evolution of the buried sediment may be related to a lower Mg/Ca concentration ratio in the oceanic system and, hence, in marine pore waters in pre-Late Jurassic times.

Thinking Architecture with an Indian Ocean Aquapelago

This article takes up the charge of thinking architecture with one of the Indian Ocean’s central coral atoll formations, the Maldives archipelago. It is undertaken as a critique of the concept of the archipelago as deployed in architecture since the 1970’s. Architects have used the archipelago as a metaphoric metageographical concept based on a land/sea binary, to conceive of architecture as autonomous from its environments. This permits the discipline exemption from its contexts and frames its engagement with the diverse mobilities of contemporary globalization. To counter this, the article draws from a broad body of literature familiar to readers of GeoHumanities, namely island studies, urban island studies, political ecology and thinking with water to undertake a reading of the Maldives as an oceanic aquapelago, as an alternative metageographical concept for architecture in today’s globalized world.

A ‘right to have rights’ in the EU public sphere? An Arendtian justification for the application of the EU Charter of Fundamental Rights

This paper discusses the Court’s reasoning in interpreting the EU Charter, using recent case law on horizontal effect as a case study. It identifies two possible means of interpreting the provisions of the Charter: firstly, an approach based on common values (e.g. equality or solidarity) and, secondly, an approach based on access to the public sphere. It argues in favour of the latter. Whereas an approach based on common values is more consonant with the development of the case law so far, it is conceptually problematic: it involves subjective assessments of the importance and degree of ‘sharedness’ of the value in question, which can undermine the equal constitutional status of different Charter provisions. Furthermore, it marginalises the Charter’s overall politically constructional character, which distinguishes it from other sources of rights protection listed in Art 6 TEU. The paper argues that, as the Charter’s provisions concretise the notion of political status in the EU, they have a primarily constitutional, rather than ethical, basis. Interpreting the Charter based on the very commitment to a process of sharing, drawing on Hannah Arendt’s idea of the ‘right to have rights’ (a right to access a political community on equal terms), is therefore preferable. This approach retains the pluralistic, post-national fabric of the EU polity, as it accommodates multiple narratives about its underlying values, while also having an inclusionary impact on previously underrepresented groups (e.g. non-market-active citizens or the sans-papiers) by recognising their equal political disposition.

Fieldworks from the Museum of the Void: Experiments in the Event of an Archive

This exhibition was a research presentation of works made at Center for Land Use Interpretation [CLUI]base in Wendover, Utah, USA between 2008-2010. The project was commissioned by the Centre For Land Interpretation in USA and funded by The Henry Moore Foundation in the UK. Documentation of research conducted in the field as made available as video and installation. An experimental discourse on the preservation of land art was put with GPS drawings and research information displayed as maps and documents. In examining physical sites in Utah, USA, the project connected to contemporary discourse centred on archives in relation to land art and land use. Using experimental processes conceived in relation to key concepts such as event structures and entropy, conceptual frameworks developed by Robert Smithson (USA) and John Latham (UK), the 'death drive' of the archive was examined in the context of a cultural impulse to preserve iconic works. The work took items from Lathams archive and placed them at the canonical 'Spiral Jetty', Smithson land art work at Rozel Point north of Salt Lake City. This became a focus for the project that also highlighted the role of the Getty Foundation in documenting major public artworks and CLUI in creating an American Land Museum. Work was created in the field at extreme remote locations using GPS technologies and visual tools were developed to articulate the concepts of the artists discussed, to engage the exhibition audience in ideas of transformation and entropy in art. Audiences were encouraged to sign a petition to be used in future preservation of spiral jetty currently facing development challenges.

On the integration of Argentinian activist art at exhibition venues

This article examines the institutional integration of activist art in the aftermath of the 2001 economic crisis in Argentina. Following this aim, we begin with a description of the most significant new groups of activist art in the City of Buenos Aires. Then, we elaborate the position these new groups take up in the field with respect to their dispute with the “light art��� from the 90s, and in relation to the mutual accusations over the “trend” of political art. Finally, we analyse the reception of these groups of activist art in art exhibitions in the City of Buenos Aires and abroad, and we reflect upon the institutionalization of these specific and situated aesthetic and political practices.

Exploring Alternative Terrain in the Rehabilitation and Treatment of Offenders: Findings from a Prison-based Music Project

The arts in prison settings have provided an alternative or complimentary component to rehabilitation. Despite increased interest, studies capturing the voice of offenders participating in projects and the long-term impact are limited. Data from semistructured interviews with 18 men who had taken part in a music-based project while incarcerated, including one group of five participants who were tracked for 18 months with supplemented data from correctional staff and official documentation, is presented. Participants of the art-based projects comment on changes they believe to have derived from participating in the project, particularly relating to emotions, self-esteem, self-confidence, communication and social skills. An exoffender sample of participants reported that participation in art projects provide experiences that promote beneficial skills that have been useful for post prison life.

Evaluating historic graffiti based on cultural significance and definitions of art.

Many examples of historic graffiti have been shown to be worthy of attention and conservation. The examples discussed in this article have been selected for their previous academic study, enabling rational assessment. This work does not suggest that only those examples of historic graffiti that have been subject to academic investigation can be evaluated and classified. This article, the result of a collaboration between two individuals with complementary interests in building conservation and contextual studies in art and design, brings together formal techniques used in the assessment of cultural significance in traditional architectural conservation and established theories in the evaluation of art. It is the purpose of this work to help those who are attempting to evaluate the merit of graffiti to do so. The current Scottish system that assesses cultural significance may be incomplete in its evaluation of graffiti. This necessitates a supplementary investigation of the artistic characteristics and merit of graffiti. Almost all graffiti could be said to be 'art', using established definitions, but not 'good' art. This evaluation may only be undertaken by experts, as with other aspects of identification of cultural significance within the built environment.

Mediterranean diet: the impact on cardiovascular risk and metabolic syndrome in HIV patients, in Lisbon, Portugal

Introduction - Metabolic syndrome (MS) is common in HIV-infected individuals and it is associated with higher cardiovascular risk (CVR). Mediterranean diet has been associated with a better metabolic control and lower CVR. Materials and methods - From December 2013 to May 2014, individuals between 18 and 65 years of age, who attended the outpatient HIV Clinic at the University Hospital Santa Maria, Lisbon, were selected. Adherence to Mediterranean diet was evaluated with MedDietScore, a scale from 0 to 55 that punctuates 11 food items according to the frequency of intake. Higher scores represent higher adherence. CVR was assessed using D.A.D tool (classified as low, moderate or high risk). We excluded individuals with opportunistic disease, hospitalized in the past three months or with renal disease diagnosis. All participants gave written informed consent. Results - In the 571 HIV patients included, 67.1% (n=383) were male, 91.6% (n=523) Caucasian, with a mean age of 46.5±8.9 years. Patients were divided in two groups: naïve (7.5%; n=43) or on antiretroviral treatment (ART) (92.5%; n=528). Mean length of HIV diagnosis was 6.7±6.5 years (naïve) and 13.3±6.1 years (ART); TCD4+ counts were above 500 cel/mm3 in 55.8% (n=24) and 67.6% (n=357) of the patients, respectively. MS was present in 33.9% (n=179) of patients in ART group and 16.3% (n=7) in naïve group. Presence of MS was associated with ART group (OR=2.7; p=0.018). MS was also associated with older age in this group (p=0.000). Overall, mean MedDietScore was 27.3±5.5. Higher score was associated with older age (r=0.319; p=0.000). Naïve patients presented a trend to higher adherence to Mediterranean diet (65.1% vs 51.7% in naïve group; p=0.090). No relation between MS and Mediterranean diet was found. Higher CVR was associated with the presence of MS in the ART group (p=0.001). In this group, individuals with moderate CVR presented higher rates of adherence to Mediterranean diet (p=0.036) when compared to low and high CVR score. Conclusions - In this cross-sectional study, naïve individuals presented a trend to higher adherence to Mediterranean diet. On the ART group, higher adherence to Mediterranean diet was found in individuals with moderate CVR score. We think that this might suggest that this group of patients adopt this diet only in the presence of metabolic alterations or perceived CVR. Prospective studies in HIV patients are required to determine the impact of adherence to Mediterranean diet on the reduction of CVR.

Frei Otto et René Sarger: entre idéaux d’architecte et vérité d’ingénieur

À travers leurs premiers écrits des années 50 et 60, Frei Otto, architecte et ingénieur allemand (1925-2015), et René Sarger (1917-1988), architecte français, n’expriment pas seulement une passion partagée des toitures suspendues. Partant du même souci d’une forme structurale « juste », leurs convictions radicales révèlent aussi les premiers questionnements des nouveaux rôles de l’ingénieur et de l’architecte de l’époque, mais aussi des idéaux opposés concernant leur position comme concepteurs et auteurs du monde bâti, ainsi que l’importance sociétale de leurs disciplines.