Intrinsic gas-phase electrophilic reactivity of Ccclic N-alkyl- and N-acyliminium ions

he intrinsic gas-phase reactivity of cyclic N-alkyl- and N-acyliminium ions toward addition of allyltrimethylsilane (ATMS) has been compared using MS2 and MS3 pentaquadrupole mass spectrometric experiments. An order of electrophilic reactivity has been derived and found to agree with orders of overall reactivity in solution. The prototype five-membered ring N-alkyliminium ion 1a and its N-CH3 analogue 1b, as well as their six-membered ring analogues 1c and 1d, lack N-acyl activation and they are, accordingly, inert toward ATMS addition. The five- and six-membered ring N-acyliminium ions with N-COCH3 exocycclic groups, 3a and 3b, respectively, are also not very reactive. The N-acyliminium ions 2a and 2c, with s-trans locked endocyclic N-carbonyl groups, are the most reactive followed closely by 3c and 3d with exocyclic (and unlocked) N-CO2CH3 groups. The five-membered ring N-acyliminium ions are more reactive than their six-membered ring analogues, that is:  2a > 2c and 3c > 3d. In contrast with the high reactivity of 2a, its N-CH3 analogue 2b is inert toward ATMS addition. For the first time, the transient intermediates of a Mannich-type condensation reaction were isolatedthe β-silyl cations formed by ATMS addition to N-acyliminium ionsand their intrinsic gas-phase behavior toward dissociation and reaction with a nucleophile investigated. When collisionally activated, the β-silyl cations dissociate preferentially by Grob fragmentation, that is, by retro-addition. With pyridine, they react competitively and to variable extents by proton transfer and by trimethylsilylium ion abstractionthe final and key step postulated for α-amidoalkylation. Becke3LYP/6-311G(d,p) reaction energetics, charge densities on the electrophilic C-2 site, and AM1 LUMO energies have been used to rationalize the order of intrinsic gas-phase electrophilic reactivity of cyclic iminium and N-acyliminium ions.

Cities at risk: status of Italian planning system in reducing seismic and hydrological risks

Italy and its urban systems are under high seismic and hydrogeological risks. The awareness about the role of human activities in the genesis of disasters is achieved in the scientific debate, as well as the role of urban and regional planning in reducing risks. The paper reviews the state of Italian major cities referred to hydrogeological and seismic risk by: 1) extrapolating data and maps about seismic hazard and landslide risk concerning cities with more than 50.000 inhabitants and metropolitan contexts, and 2) outlining how risk reduction is framed in Italian planning system (at national and regional levels). The analyses of available data and the review of the normative framework highlight the existing gaps in addressing risk reduction: nevertheless a wide knowledge about natural risks afflicting Italian territory and an articulated regulatory framework, the available data about risks are not exhaustive, and risk reduction policies and multidisciplinary pro-active approaches are only partially fostered and applied.

Using technology to overcome the tyranny of space: information provision and wayfinding.

Urban wayfinding technology offers many possibilities by which older people and mobility-impaired users can overcome the barriers encountered on every-day journeys in the built environment. Previous work has highlighted the extent to which personal mobility and independence are significant determinants of the quality of life amongst both elderly and visually impaired groups. The paper outlines the development of the auditory location finder (ALF), which is a beacon-based local information system designed to enhance the wayfinding activities of these, and potentially other, user-groups in the community. The proposed system provides the user with an audio message, which is obtained on request via a small portable hand unit. The messages inform the user of their whereabouts and give information about the area that they are currently in. The development of the device involves issues such as message content and structure, route choice, orientation, landmarks, clues and the extent of user reliance on technology. Preliminary trials have been carried out in a UK city and have obtained initial user feedback to help underpin the technological development of the device and its potential application. The paper concludes by outlining the importance of new urban technology and the way in which such local information systems can potentially contribute to overcoming particular patterns of exclusion experienced by mobility-impaired groups, such as the visually impaired

Urban ponds as an aquatic biodiversity resource in modified landscapes.

Urbanization is a global process contributing to the loss and fragmentation of natural habitats. Many studies have focused on the biological response of terrestrial taxa and habitats to urbanization. However, little is known regarding the consequences of urbanization on freshwater habitats, especially small lentic systems. In this study we examined aquatic macroinvertebrate diversity (family and species level) and variation in community composition between 240 urban and 784 non-urban ponds distributed across the UK. Contrary to predictions, urban ponds supported similar numbers of invertebrate species and families compared to non-urban ponds. Similar gamma diversity was found between the two groups at a family level, and while at a species level gamma diversity was higher in non-urban ponds, this difference was not statistically significant. The biological communities of urban ponds were markedly different to those of non-urban ponds and the variability in urban pond community composition was greater than that in non-urban ponds, contrary to previous work showing homogenisation of communities in urban areas. Positive spatial autocorrelation was recorded for urban and non-urban ponds at 0-50 km (distance between pond study sites) and negative spatial autocorrelation was observed at 100-150 km, and was stronger in urban ponds in both cases. Ponds do not follow the same ecological patterns as terrestrial and lotic habitats (reduced taxonomic richness) in urban environments; in contrast they support high taxonomic richness and contribute significantly to regional faunal diversity. Individual cities are complex structural mosaics which evolve over long periods of time and are managed in diverse ways, promoting the development of a wide-range of environmental conditions and habitat niches in urban ponds which can promote greater heterogeneity between pond communities at larger scales. Ponds provide an opportunity for managers and environmental regulators to conserve and enhance freshwater biodiversity in urbanized landscapes whilst also facilitating key ecosystem services including storm water storage and water treatment.

Budowa, asymetria i dymorfizm płciowy stawu ramiennego w populacji średniowiecznej i współczesnej

Wydział Biologii: Instytut Antropologii

Cone penetration testing to assess slope stability in the 1979 Nice landslide area (Ligurian Margin, SE France)

In the landslide-prone area near the Nice international airport, southeastern France, an interdisciplinary approach is applied to develop realistic lithological/geometrical profiles and geotechnical/strength sub-seafloor models. Such models are indispensable for slope stability assessments using limit equilibrium or finite element methods. Regression analyses, based on the undrained shear strength (su) of intact gassy sediments are used to generate a sub-seafloor strength model based on 37 short dynamic and eight long static piezocone penetration tests, and laboratory experiments on one Calypso piston and 10 gravity cores. Significant strength variations were detected when comparing measurements from the shelf and the shelf break, with a significant drop in su to 5.5 kPa being interpreted as a weak zone at a depth between 6.5 and 8.5 m below seafloor (mbsf). Here, a 10% reduction of the in situ total unit weight compared to the surrounding sediments is found to coincide with coarse-grained layers that turn into a weak zone and detachment plane for former and present-day gravitational, retrogressive slide events, as seen in 2D chirp profiles. The combination of high-resolution chirp profiles and comprehensive geotechnical information allows us to compute enhanced 2D finite element slope stability analysis with undrained sediment response compared to previous 2D numerical and 3D limit equilibrium assessments. Those models suggest that significant portions (detachment planes at 20 m or even 55 mbsf) of the Quaternary delta and slope apron deposits may be mobilized. Given that factors of safety are equal or less than 1 when further considering the effect of free gas, a high risk for a landslide event of considerable size off Nice international airport is identified

The interpersonal and mental health implications of the coherence of coming out narratives for a sample of gay men in committed romantic relationships

The coming out process has been conceptualized as a developmental imperative for those who will eventually accept their same-sex attractions. It is widely accepted that homophobia, heterosexism, and homonegativity are cultural realities that may complicate this developmental process for gay men. The current study views coming out as an extra-developmental life task that is at best a stressful event, and at worst traumatic when coming out results in the rupture of salient relationships with parents, siblings, and/or close friends. To date, the minority stress model (Meyer, 1995; 2003) has been utilized as an organizing framework for how to empirically examine external stressors and mental health disparities for lesbians, gay men, and bisexual individuals in the United States. The current study builds on this literature by focusing on the influence of how gay men make sense of and represent the coming out process in a semi-structured interview, more specifically, by examining the legacy of the coming out process on indicators of wellness. In a two-part process, this study first employs the framework well articulated in the adult attachment literature of coherence of narratives to explore both variation and implications of the coming out experience for a sample of gay men (n = 60) in romantic relationships (n = 30). In particular, this study employed constructs identified in the adult attachment literature, namely Preoccupied and Dismissing current state of mind, to code a Coming Out Interview (COI). In the present study current state of mind refers to the degree of coherent discourse produced about coming out experiences as relayed during the COI. Multilevel analyses tested the extent to which these COI dimensions, as revealed through an analysis of coming out narratives in the COI, were associated with relationship quality, including self-reported satisfaction and observed emotional tone in a standard laboratory interaction task and self-reported symptoms of psychopathology. In addition, multilevel analyses also assessed the Acceptance by primary relationship figures at the time of disclosure, as well as the degree of Outness at the time of the study. Results revealed that participant’s narratives on the COI varied with regard to Preoccupied and Dismissing current state of mind, suggesting that the AAI coding system provides a viable organizing framework for extracting meaning from coming out narratives as related to attachment relevant constructs. Multilevel modeling revealed construct validity of the attachment dimensions assessed via the COI; attachment (i.e., Preoccupied and Dismissing current state of mind) as assessed via the Adult Attachment Interview (AAI) was significantly correlated with the corresponding COI variables. These finding suggest both methodological and conceptual convergence between these two measures. However, with one exception, COI Preoccupied and Dismissing current state of mind did not predict relationship outcomes or self-reported internalizing and externalizing symptoms. However, further analyses revealed that the degree to which one is out to others moderated the relationship between COI Preoccupied and internalizing. Specifically, for those who were less out to others, there was a significant and positive relationship between Preoccupied current state of mind towards coming out and internalizing symptoms. In addition, the degree of perceived acceptance of sexual orientation by salient relationship figures at the time of disclosure emerged as a predictor of mental health. In particular, Acceptance was significantly negatively related to internalizing symptoms. Overall, the results offer preliminary support that gay men’s narratives do reflect variation as assessed by attachment dimensions and highlights the role of Acceptance by salient relationship figures at the time of disclosure. Still, for the most part, current state of mind towards coming out in this study was not associated with relationship quality and self-reported indicators of mental health. This finding may be a function of low statistical power given the modest sample size. However, the relationship between Preoccupied current state of mind and mental health (i.e., internalizing) appears to depend on degree of Outness. In addition, the response of primary relationships figures to coming out may be a relevant factor in shaping mental health outcomes for gay men. Limitations and suggestions for future research and clinical intervention are offered.

Performance Energética no contexto do sistema LEED

Com o aumento constante de procura de recursos naturais por parte dos vários setores da sociedade é urgente encontrar soluções para reduzir o seu consumo sem se travar a expansão demográfica que se tem vindo a sentir nos grandes centros urbanos. É através da implementação de medidas de sustentabilidade e pelo aumento da eficiência de utilização desses recursos que se tem vindo a combater esta tendência cada vez maior de consumismo global, sendo isto apenas possível com a implementação de ferramentas tecnológicas avançadas que permitem estabelecer limites ao considerado eficiente e premiando, em termos financeiros e de imagem de marketing, as entidades que o alcancem. O LEED é um sistema de certificação de sustentabilidade voluntário de edifícios residenciais e comerciais que estabelece métricas de comparação de parâmetros indicadores de consumos energéticos, hídricos e de materiais em todo o ciclo de vida do edifício e que tem vindo a ganhar destaque em crescendo a nível mundial. Esta dissertação teve como objetivo comparar a performance de consumo energético no âmbito do sistema LEED com a do sistema de certificação energética de edifícios nacional (SCE) de um grande edifício de serviços, estabelecendo um paralelismo de semelhanças e diferenças entre os dois e de avaliar os efeitos de potenciais medidas de eficiência energética e seus efeitos nas classificações de mérito obtidas em cada sistema. Os resultados obtidos na simulação que permitiu avaliar a performance foi muito satisfatório, tendo sido aproveitado pela empresa para efeitos de certificação LEED do edifício em estudo.

MOWING TO GROWING: TRANSFORMING A MUNICIPAL GOLF COURSE TO URBAN AGRICULTURE IN BALTIMORE CITY

This thesis demonstrates how landscape architects can transform underused golf course facilities located within cities for urban agriculture (UA). In the last decade more than 1000 golf courses have closed in the United States. Municipal golf courses represent some of the largest pieces of open space in cities and because of their inherent infrastructure they can provide the ideal location to support large-scale UA. In Southwest Baltimore large food deserts are a serious health concern and represent a lack of access to healthy food options for residents. Carroll Urban Agriculture Park is a design response resulting from a detailed analysis of the existing Carroll Park Golf Course and the surrounding community of Southwest Baltimore. The design will create an urban farm in a park-like setting to provide readily accessible healthy food options and various educational opportunities, and to support current and future urban agriculture related businesses in Baltimore.

Integrated visual perception architecture for robotic clothes perception and manipulation

This thesis proposes a generic visual perception architecture for robotic clothes perception and manipulation. This proposed architecture is fully integrated with a stereo vision system and a dual-arm robot and is able to perform a number of autonomous laundering tasks. Clothes perception and manipulation is a novel research topic in robotics and has experienced rapid development in recent years. Compared to the task of perceiving and manipulating rigid objects, clothes perception and manipulation poses a greater challenge. This can be attributed to two reasons: firstly, deformable clothing requires precise (high-acuity) visual perception and dexterous manipulation; secondly, as clothing approximates a non-rigid 2-manifold in 3-space, that can adopt a quasi-infinite configuration space, the potential variability in the appearance of clothing items makes them difficult to understand, identify uniquely, and interact with by machine. From an applications perspective, and as part of EU CloPeMa project, the integrated visual perception architecture refines a pre-existing clothing manipulation pipeline by completing pre-wash clothes (category) sorting (using single-shot or interactive perception for garment categorisation and manipulation) and post-wash dual-arm flattening. To the best of the author’s knowledge, as investigated in this thesis, the autonomous clothing perception and manipulation solutions presented here were first proposed and reported by the author. All of the reported robot demonstrations in this work follow a perception-manipulation method- ology where visual and tactile feedback (in the form of surface wrinkledness captured by the high accuracy depth sensor i.e. CloPeMa stereo head or the predictive confidence modelled by Gaussian Processing) serve as the halting criteria in the flattening and sorting tasks, respectively. From scientific perspective, the proposed visual perception architecture addresses the above challenges by parsing and grouping 3D clothing configurations hierarchically from low-level curvatures, through mid-level surface shape representations (providing topological descriptions and 3D texture representations), to high-level semantic structures and statistical descriptions. A range of visual features such as Shape Index, Surface Topologies Analysis and Local Binary Patterns have been adapted within this work to parse clothing surfaces and textures and several novel features have been devised, including B-Spline Patches with Locality-Constrained Linear coding, and Topology Spatial Distance to describe and quantify generic landmarks (wrinkles and folds). The essence of this proposed architecture comprises 3D generic surface parsing and interpretation, which is critical to underpinning a number of laundering tasks and has the potential to be extended to other rigid and non-rigid object perception and manipulation tasks. The experimental results presented in this thesis demonstrate that: firstly, the proposed grasp- ing approach achieves on-average 84.7% accuracy; secondly, the proposed flattening approach is able to flatten towels, t-shirts and pants (shorts) within 9 iterations on-average; thirdly, the proposed clothes recognition pipeline can recognise clothes categories from highly wrinkled configurations and advances the state-of-the-art by 36% in terms of classification accuracy, achieving an 83.2% true-positive classification rate when discriminating between five categories of clothes; finally the Gaussian Process based interactive perception approach exhibits a substantial improvement over single-shot perception. Accordingly, this thesis has advanced the state-of-the-art of robot clothes perception and manipulation.

La biodiversidad urbana como síntoma de una ciudad sostenible. Estudio de la zona del Yanuncay en Cuenca, Ecuador

Al testear la situación de la biodiversidad urbana y los espacios verdes en la zona del Yanuncay de Cuenca (Ecuador), se pretendió revelar particularidades de la co-determinación entre la biodiversidad y las áreas verdes al interior de la ciudad. Se calcularon seis indicadores y tres índices que mostraron niveles alarmantemente bajos, que sugieren la necesidad de acciones inmediatas con el fin de recuperar la biodiversidad perdida. Por ejemplo, en el caso del indicador de la Permeabilidad del Suelo Público el 83.53% del suelo no es permeable; en cuanto a la Proximidad a Espacios Verdes el 98.82% del área de estudio no se aproxima al objetivo mínimo; en lo referente al cálculo de la Densidad de Árboles por Tramo de Calle el 98.83% de los tramos tienen arbolado insuficiente. Un aporte importante del trabajo es la construcción del Índice de Verde Urbano (IVU) que conjuga el indicador de Superficie Verde por Habitante con el de Proximidad Simultánea a Tres Tipos de Espacios Verdes, de este modo se puede tener una mirada tanto de la cantidad como de la cobertura e influencia, a distintas escalas, que estas áreas tienen sobre las personas. En este índice se constata que el 91.76% del área no cumple con el valor mínimo. Estos datos nos permiten afirmar que la ciudad actual y su producción de áreas verdes no contribuyen a la sostenibilidad ecológica y por ende a la biodiversidad urbana. Si no se proponen cambios urgentes al modelo de ciudad vigente, estos valores se volverán aún más alarmantes.

Validity and reliability of the Cyber-aggression Questionnaire for Adolescents (CYBA)

Cybercrime is a growing and worrisome problem, particularly when it involves minors. Cyber-aggression among adolescents in particular can result in negative legal and psychological consequences for people involved. Therefore, it is important to have instruments to detect these incidents early and understand the problem to propose effective measures for prevention and treatment. This paper aims to design a new self-report, the Cyber-Aggression Questionnaire for Adolescents (CYBA), to evaluate the extent to which the respondent conducts aggressions through a mobile phone or the internet and analyse the factorial and criterion validity and reliability of their scores in a sample of adolescents from Asturias, Spain. The CYBA was administered to 3,148 youth aged between 12 and 18 years old along with three self-reports to measure aggression at school, impulsivity, and empathy. Regarding factorial validity, the model that best represents the structure of the CYBA consists of three factors (Impersonation, Visual-sexual Cyber-aggression, and Verbal Cyber-aggression and Exclusion) and four additional indicators of Visual Cyber-aggression-Teasing/Happy Slapping. Regarding criterion validity, the score on the CYBA correlates positively with aggression at school and impulsivity and negatively with empathy. That is the way cyber-aggression correlates with these three variables, according to previous empirical evidence. The reliability of the scores on each item and factor of the CYBA are adequate. Therefore, the CYBA offers a valid and reliable measure of cyber-aggression in adolescents.

Avaliação da disponibilidade de espaços verdes públicos no contexto urbano e a sua relação com a perceção dos residentes. Um estudo para a cidade de Bragança

Os espaços verdes públicos urbanos são muito importantes no contexto urbano. Influenciam de diversas formas na qualidade de vida das populações, proporcionando benefícios ambientais, sociais e econômicos. A fim de avaliar a disponibilidade destes espaços na cidade de Bragança, foram realizadas análises utilizando indicadores, com apoio dos software ArcGIS 9.3 e QGis 2.14.0-Essen, que permitiram avaliar a oferta destes espaços nas suas diferentes tipologias e categorias dimensionais. Para o efeito foram aplicados os indicadores: Percentagem de espaços verdes, Espaços verdes per capita, Distância média, Índice de Área Verde por Área de Implantação e Índice de Área Verde por Área Coberta. Posteriormente, procedeu-se à aplicação de inquéritos a fim de avaliar as perceções e atitudes de uma amostra da população de Bragança, realizando análises descritivas e estatísticas, com recurso ao software SPSS17, buscando descrever a atual relação com os espaços verdes e usando testes não paramétricos para identificar diferenças entre subgrupos da amostra, numa análise centrada em dois níveis: a escala urbana e a escala de Bairro. Procurando avaliar possíveis alterações futuras, foram testados cenários realistas, um correspondendo à introdução de espaços verdes em terrenos na posse da Autarquia e outro considerando a ampliação das áreas verdes previstas no Plano de Urbanização de Bragança de 2010. Os Resultados permitiram identificar diferenças relevantes na oferta de espaços verdes da cidade. Aplicando os indicadores foi possível verificar que existe a concentração de espaços verdes de maior dimensão na zona central da cidade, denotando um claro desequilíbrio na introdução de novos espaços em zonas de expansão urbana. Os inquéritos aplicados possibilitaram constatar que os inquiridos que possuem maior disponibilidade de espaços verdes em seu bairro de residência apresentam respostas mais satisfatórias em relação a acessibilidade e a aparência visual e paisagística dos bairros. Da análise de cenários resulta que com a implantação de novos espaços verdes, para as duas análises, ocorreria uma melhoria da oferta e distribuição dos espaços verdes na cidade permitindo um maior reequilíbrio face à concentração na zona central, melhorando a acessibilidade para toda a população.

Relationship between subjective wellbeing and weight perception in children and adolescents: Gender and age differences

The relation between weight status (Body Mass Index - BMI), weight perception and subjective wellbeing remains unclear. Several studies conclude that discrepancies can be found between weight status and weight perception, among children and adolescents. The present study aims at investigating the associations between subjective wellbeing and individual characteristics, among children and adolescents. The sample included 1200 children and adolescents (51.7 % girls, aged 9 to 17). Their mean age was 12.55 years (SD = 1.61). The questionnaire was completed in school context, asking about the subjective wellbeing, use of self-regulation, eating behavior awareness/care, weight perception and sociodemographic questions such as age, gender and BMI. The study found a strong association between BMI and weight perception, although subjective wellbeing was better explained by weight perception than by BMI. Eating awareness and self-regulation also played an important role in subjective controlling for age and gender. Age and gender interfere in the relation between subjective wellbeing and other variables. The multiple regression model is more robust and explicative for girls and older children. Psychological factors related to weight, such as weight perception, self-regulation and eating awareness have a stronger explicative impact in subjective wellbeing compared to physical aspects, such as Body Mass Index. The relation between subjective wellbeing and weight is influence by age and gender.

Del videojuego a la realidad : sistema interactivo para la seguridad vial

El vertiginoso crecimiento de los centros urbanos, las tecnologías emergentes y la demanda de nuevos servicios por parte de la población plantea encaminar esfuerzos hacia el desarrollo de las ciudades inteligentes. Éste concepto ha tomado fuerza entre los sectores político, económico, social, académico, ambiental y civil; de forma paralela, se han generado iniciativas que conducen hacia la integración de la infraestructura, la tecnología y los servicios para los ciudadanos. En éste contexto, una de las problemáticas con mayor impacto en la sociedad es la seguridad vial. Es necesario contar con mecanismos que disminuyan la accidentalidad, mejoren la atención a incidentes, optimicen la movilidad urbana y planeación municipal, ayuden a reducir el consumo de combustible y la emisión de gases de efecto de invernadero, así como ofrecer información dinámica y efectiva a los viajeros. En este artículo se describen dos (2) enfoques que contribuyen de manera eficiente dicho problema: los videojuegos como juegos serios y los sistemas de transporte inteligente. Ambos enfoques están encaminados a evitar colisiones y su diseño e implementación requieren componentes altamente tecnológicos (e.g. sistemas telemáticos e informáticos, inteligencia artificial, procesamiento de imágenes y modelado 3D).