Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

La participación de la mujer en las Misiones de Paz de Naciones Unidas a través de la actuación de las FF.AA

Resumen: El presente estudio es de Alcance temporal Transversal ygrado de conocimientoDescriptivo. Su tipo de diseño es Cuantitativo, acorde a la lógica de investigación Analítico-Empírica. Recurre a la Investigación Documental e Investigación de Campo. El tipo de muestreo es No Probabilístico, la selección de la muestra es Intencional, y la Unidad de Análisis es El Grado de Integración de las FFAA en cuestiones de Género. El instrumento releva tres Dimensiones: 1. Nivel de integración de género. 2. Posibilidades de desarrollo de carrera y profesional dentro de las Fuerzas Armadas para la mujer. 3. Limitaciones para el desarrollo de la mujer en las Fuerzas Armadas. Se observa en el presente, el nivel de integración de género alcanzado en las misiones de paz de la ONU1, su incidencia en la labor de dichos grupos, y los cambios que ello ha implicado en las Fuerzas Armadas que participan de dichas operaciones internacionales. Asimismo, a fin de considerar el alcance de dicha integración de la mujer en una institución tradicionalmente masculina, se ha considerado pertinente conocer qué dificultades han encontrado para alcanzar la igualdad de trato y oportunidades, a fin de conocer qué aspectos resta mejorar a fin de lograr la participación femenina en las Fuerzas Armadas nacionales y en las misiones de paz, en igualdad de condiciones. Para ello, se ha encuestado la cantidad de 47 hombres y mujeres de las Fuerzas Armadas Argentinas que han participado o que aspiran a participar de las misiones de paz de la Organización de las Naciones Unidas en el mundo, a fin de conocer sus experiencias, apreciaciones y expectativas. El instrumento ha sido diseñado ad hoc para el presente trabajo, para conocer la experiencia de hombres y mujeres de las misiones de paz argentinas en el mundo, respecto del nivel y eficacia de la integración de género. Este tema cumple con los requisitos de estudiar la participación de población local en actividades de relaciones internacionales, dado que se forman en las instituciones locales, y se desempeñan en distintos puntos del globo, como Haití, Líbano o Medio Oriente, representando a la Argentina. Se han obtenido los siguientesResultados: Se ha obtenido una muestra equilibrada en materia de edades. Las mujeres, en un margen del 1 al 10, consideran que la integración de la mujer en las FFAA alcanza una puntuación media (6.96). Los hombres le asignan un puntaje más alto (8.48). En su evaluación de la importancia de la participación de la mujer en las Misiones de Paz, ambos han asignado un puntaje alto (entre 7 y 9) Un 58.3% de las mujeres consideran que la mujer sufre desventajas y limitaciones en la institución, mientras que un 73.9% sostiene, en cambio, que gozan de privilegios, y ningún hombre ha considerado que sufran desventajas y limitaciones. La percepción al respecto es opuesta en ambos géneros. En cuanto a los tratos diferenciados, el 100% de los hombres consideran que existe igualdad en las posibilidades de ascenso; mientras que un 50% aproximadamente sostiene que la exigencia en la Instrucción y Tareas en las Mujeres es equitativa y que éstas reciben un trato menos riguroso que el hombre. Un 73.9% sostiene que existe equidad en la expectativa en las mujeres. Las mujeres tienen, respecto a estos aspectos, percepciones divididas, lo que permite apreciar diversidad en las experiencias vividas por éstas y heterogeneidad en el trato recibido: mientras que porcentajes entre 50 y 80% consideran igualdad en los tratos recibidos; porcentajes cercanos al 25 y 30% consideran que tienen menores posibilidades de ascenso, menor exigencia en tareas y evaluación y menor trato riguroso. Porcentajes de entre 12 y 30%, en cambio, consideran que la exigencia y el trato son superiores para la mujer. Para ambos géneros, la incorporación de las mujeres a las FFAA ha sido positiva, aunque algunos hombres (26.1%) la consideran negativa. Asimismo, mientras que un 73.9% de hombres calificarían el desempeño de la mujer como igual al del hombre; el 75% de las mujeres lo consideran diferente y complementario. En cuanto a las ventajas en al conformación de equipos mixtos en las misiones de paz, las mujeres han mostrado una visión estereotipada de sí mismas, valorando tareas de asistencia y cuidado, mientras el los hombres han valorado su participación para el éxito de la misión, para mejorar relaciones con la población local y otras variadas. Los hombres han reconocido la existencia de limitaciones para el desarrollo de la mujer en su carrera militar, como el machismo, la discriminación y las restricciones para el ascenso, mientras que las mujeres se centran en la maternidad y el rechazo al liderazgo femenino como principales problemas.Se concluye en el presente que: La participación de la mujer en las Fuerzas Armadas y en las misiones de paz de Argentina son alarmantemente insuficientes. Sus niveles de participación son mínimos. La necesidad de la integración de género es creciente, dado que se su presencia en las misiones de paz resulta fundamental para establecer vínculos con las poblaciones locales, empoderar a sus mujeres y atender a las necesidades de personas vulneradas bajo todo tipo de violencia. Las Fuerzas Armadas se pueden beneficiar de la integración de género, ya que se trata de una institución eminentemente heterogénea. Las misiones de paz resultan un espacio ideal para incorporar la perspectiva de género y encontrar soluciones creativas a los conflictos que la institución debe enfrentar en todos los ámbitos

Calidad de vida en adultos con diagnóstico de psoriasis de la ciudad de Paraná : diferencias según sexo

Resumen: La presente investigación tuvo como objetivo evaluar la percepción de la calidad de vida en aquellos adultos con diagnóstico de psoriasis de la ciudad de Paraná y conocer diferencias según sexo. El diseño de investigación fue de tipo descriptivo – correlacional, transversal y de campo; el muestreo fue intencional no probabilístico. Con una muestra compuesta por 36 sujetos de ambos sexo, de 18 a 65 años. Los instrumentos que se aplicaron fueron el World Health Organization Quality of Life Questionaire (WHOQOL-100), en su versión Argentina (Bonicatto y Soria, 1998), junto con dos cuestionarios ad hoc, uno sociodemográfico y otro para explorar la imagen corporal. El procesamiento de la información obtenida a través del WHOQOL-100 se realizó mediante el programa Stadistical Package for the Social Sciences (SPSS) 21. Mientras que los ítems del cuestionario ad hoc de imagen corporal fueron evaluados cualitativamente de manera individual, las respuestas fueron agrupadas por categorías y luego se obtuvieron las frecuencias, porcentajes y análisis de contenido. Se observó que los adultos con diagnóstico de psoriasis de la ciudad de Paraná presentaron en general, una buena calidad de vida. Se determinó que existen diferencias según sexo, las mujeres obtuvieron mayores puntajes en los dominios Relaciones Sociales y Espiritualidad, como también en las facetas de sentimientos positivos, relaciones personales, seguridad física y espiritualidad. Por último, se observó que la imagen corporal se vio afectada por dicha enfermedad en la muestra estudiada

Del combate singular al singular combate sexual en la sátira trovadoresca medieval gallego-portuguesa

Integran este número de la revista ponencias presentadas en Studia Hispanica Medievalia VIII: Actas de las IX Jornadas Internacionales de Literatura Española Medieval, 2008, y de Homenaje al Quinto Centenario de Amadis de Gaula.

PPs without Disguises: Reply to Bruening

[EN]Bresnan and Nikitina (2009) and Rappaport Hovav and Levin (2008) show that, contrary to standard assumptions, fixed-theme idioms may appear in to-constructions under certain pragmatic circumstances. Bruening (2010a) contends that the cases they present are in fact R(ightward)-dative shifts, double object constructions with the object projected to the right. In this article, we argue that Bruening’s proposed theoretical apparatus is unnecessarily complex and ad hoc and falls short of explaining the main facts it is supposed to deal with, massively overgenerating. A regular PP structure is argued to be empirically more adequate and conceptually simpler, avoiding the main problems of the R-dative shift analysis. New empirical evidence concerning pairlist readings and scope freezing also suggests that the empirical facts about idioms should be reconsidered in completely different terms.

Pautas de conducta constructiva en psicomotricidad a los dos años

[Es]Este trabajo forma parte de una investigación empírica que aplica la metodología observacional a la incipiente actividad constructiva propia de la psicomotricidad espontánea a los dos años de edad. Es un estudio idiográfico, el diseño observacional utilizado es nomotético, de seguimiento y multidimensional. El instrumento de observación desarrollado ad hoc para el registro de la conducta conscontructiva es el formato de campo “la construcción en psicomotricidad durante el tercer año de vida”. La fiabilidad del instrumento se establece a partir del grado de concordancia entre los observadores. Los resultados, obtenidos mediante el análisis de coocurrencias, informan sobre las condiciones, modalidades, tendencias, evolución y niveles de acción que estas primeras conductas constructivas despliegan. Esta actividad de construcción, de acuerdo con la teoría psicogenética walloniana, puede ser considerada invención de nuevas conductas adecuadas a las nuevas situaciones. Su suspensión da lugar a símbolos enactivos, precursores del juego simbólico infantil.

International Workshop for Management and Trade of Caiman yacare, Gainsville, FL, 3-5 October 2002

A workshop was held 3-5 October 2002 in Gainesville, Florida, USA to discuss management, conservation and trade in Caiman yacare. Twenty five official participants represented the four yacare range states (Argentina, Bolivia, Brazil, Paraguay), Venezuela, USA, the meeting sponsors (US Fish and Wildlife Service, CITES Secretariat, Louisiana Fur and Alligator Council), TRAFFIC Sur America and Crocodile Specialist Group. A series of country reports detailing yacare management in the four range states were distributed in Spanish and English prior to the meeting and presentations on these and on general principles of crocodilian harvest, conservation and management provided the basis for the discussions. Three working groups considered: • Requirements and field techniques for field data collection. • Requirements and techniques for regulation of harvest. • Requirements and processes for regulation of trade and export. Written reports of working groups and a plenary drafting session were finalized during the meeting and distributed, with the country reports, to participants. The workshop drafted a framework for caiman management and regulation that could be used as a template and adapted for use in each range state. The meeting agreed to convene an ad-hoc working group of range state representatives to continue discussions on the harmonization of caiman management into the future.

Mikroblogintza tekniken erabilera programazioan sortzen diren zalantzak ebazteko

Gaur egun Twitter moduko mikroblogintza aplikazioak zalantzak argitzeko gero eta gehiago erabiltzen dira. Erabiltzaileak laguntza eskaera adierazi eta sare sozialaren bidez bere kontaktuei helarazi egiten zaie. Erabiltzaileak galdera eta erantzunen kudeaketa sare sozial nahaste baten barruan egin beharko du. Proiektuaren helburu nagusia mikroblogintza plataformetako kanala programazio lengoaien IDEen barruan bateratzea da, modu honetan laguntza eskatzeko prozesua IDEetan bertan kudeatzeko.

Efficient methods for empirical tests of behavioral economics theories in laboratory and field experiments

In the quest for a descriptive theory of decision-making, the rational actor model in economics imposes rather unrealistic expectations and abilities on human decision makers. The further we move from idealized scenarios, such as perfectly competitive markets, and ambitiously extend the reach of the theory to describe everyday decision making situations, the less sense these assumptions make. Behavioural economics has instead proposed models based on assumptions that are more psychologically realistic, with the aim of gaining more precision and descriptive power. Increased psychological realism, however, comes at the cost of a greater number of parameters and model complexity. Now there are a plethora of models, based on different assumptions, applicable in differing contextual settings, and selecting the right model to use tends to be an ad-hoc process. In this thesis, we develop optimal experimental design methods and evaluate different behavioral theories against evidence from lab and field experiments.

We look at evidence from controlled laboratory experiments. Subjects are presented with choices between monetary gambles or lotteries. Different decision-making theories evaluate the choices differently and would make distinct predictions about the subjects' choices. Theories whose predictions are inconsistent with the actual choices can be systematically eliminated. Behavioural theories can have multiple parameters requiring complex experimental designs with a very large number of possible choice tests. This imposes computational and economic constraints on using classical experimental design methods. We develop a methodology of adaptive tests: Bayesian Rapid Optimal Adaptive Designs (BROAD) that sequentially chooses the "most informative" test at each stage, and based on the response updates its posterior beliefs over the theories, which informs the next most informative test to run. BROAD utilizes the Equivalent Class Edge Cutting (EC²) criteria to select tests. We prove that the EC² criteria is adaptively submodular, which allows us to prove theoretical guarantees against the Bayes-optimal testing sequence even in the presence of noisy responses. In simulated ground-truth experiments, we find that the EC² criteria recovers the true hypotheses with significantly fewer tests than more widely used criteria such as Information Gain and Generalized Binary Search. We show, theoretically as well as experimentally, that surprisingly these popular criteria can perform poorly in the presence of noise, or subject errors. Furthermore, we use the adaptive submodular property of EC² to implement an accelerated greedy version of BROAD which leads to orders of magnitude speedup over other methods.

We use BROAD to perform two experiments. First, we compare the main classes of theories for decision-making under risk, namely: expected value, prospect theory, constant relative risk aversion (CRRA) and moments models. Subjects are given an initial endowment, and sequentially presented choices between two lotteries, with the possibility of losses. The lotteries are selected using BROAD, and 57 subjects from Caltech and UCLA are incentivized by randomly realizing one of the lotteries chosen. Aggregate posterior probabilities over the theories show limited evidence in favour of CRRA and moments' models. Classifying the subjects into types showed that most subjects are described by prospect theory, followed by expected value. Adaptive experimental design raises the possibility that subjects could engage in strategic manipulation, i.e. subjects could mask their true preferences and choose differently in order to obtain more favourable tests in later rounds thereby increasing their payoffs. We pay close attention to this problem; strategic manipulation is ruled out since it is infeasible in practice, and also since we do not find any signatures of it in our data.

In the second experiment, we compare the main theories of time preference: exponential discounting, hyperbolic discounting, "present bias" models: quasi-hyperbolic (α, β) discounting and fixed cost discounting, and generalized-hyperbolic discounting. 40 subjects from UCLA were given choices between 2 options: a smaller but more immediate payoff versus a larger but later payoff. We found very limited evidence for present bias models and hyperbolic discounting, and most subjects were classified as generalized hyperbolic discounting types, followed by exponential discounting.

In these models the passage of time is linear. We instead consider a psychological model where the perception of time is subjective. We prove that when the biological (subjective) time is positively dependent, it gives rise to hyperbolic discounting and temporal choice inconsistency.

We also test the predictions of behavioral theories in the "wild". We pay attention to prospect theory, which emerged as the dominant theory in our lab experiments of risky choice. Loss aversion and reference dependence predicts that consumers will behave in a uniquely distinct way than the standard rational model predicts. Specifically, loss aversion predicts that when an item is being offered at a discount, the demand for it will be greater than that explained by its price elasticity. Even more importantly, when the item is no longer discounted, demand for its close substitute would increase excessively. We tested this prediction using a discrete choice model with loss-averse utility function on data from a large eCommerce retailer. Not only did we identify loss aversion, but we also found that the effect decreased with consumers' experience. We outline the policy implications that consumer loss aversion entails, and strategies for competitive pricing.

In future work, BROAD can be widely applicable for testing different behavioural models, e.g. in social preference and game theory, and in different contextual settings. Additional measurements beyond choice data, including biological measurements such as skin conductance, can be used to more rapidly eliminate hypothesis and speed up model comparison. Discrete choice models also provide a framework for testing behavioural models with field data, and encourage combined lab-field experiments.

Calibration of Grassholme Channels, 1982

Adjustment of experimental channels to give any specified pattern of water depth or velocity is complex and tedious because it involves a number of variables. Since some variables are not controllable and variables may interact, valve settings of the Grassholme channels were initially determined on an ad hoc basis to suit individual experiments. This method was used during 1982 but additional observations were made in order to gain more detailed understanding of the channel system and, as far as possible, to develop a guide to future short-cuts in attaining suitable channel settings for any given purpose. This report describes calibration of the Grassholme channels (using water of the Grassholme Reservoir) for the biological experiments of spring - summer 1982. The main variables that are discussed are valve turns and discharge and velocity and depth. It also seeks to establish relationships which will be of value in future managment of the channels for experimental purposes.

A política pública de emprego: entre a pracarização desprotegida e a precarização protegida. Um estudo comparativo entre Brasil e Itália

Este trabalho discute a política de emprego implementada no Brasil e na Itália nos últimos 10 anos. A ideia central é de que a política de emprego vem sendo alvo de estratégias por parte do Estado brasileiro e italiano como forma de responder ao problema endêmico do desemprego e se encontra dentro das exigências propostas pelas agências multilaterais para minimizar os impactos das mudanças em curso no âmbito do trabalho. Embora o desemprego sempre tenha sido um elemento fundamental na dinâmica das relações sociais de produção capitalista, tendo em vista que a formação de um excedente de trabalhadores é condição fundamental para a extração da taxa de mais-valia, através do trabalho não pago e expropriado pelo capitalista, ele vem sendo considerado como um processo natural, sem qualquer vinculação com a lógica da acumulação capitalista e, portanto, as políticas de emprego revelam-se como medidas pontuais que tendem a responsabilizar os sujeitos pela sua "incapacidade" de se adequar às mudanças em curso. neste sentido, as ações propostas reforçam o incentivo ao empreendedorismo, a precarização das condições de trabalho, no incremento do trabalho feminino e juvenil e na retirada gradativa de direitos sociais e trabalhistas. As consequências não podem ser percebidas igualmente nos dois países, haja vista as condições sócio-históricas que deram luz ao Estado social permitindo que na Itália as mudanças em curso apontem para uma precarização protegida e no Brasil numa precarização desprotegida.

Evaluación de la actividad científica: conectividad relevante y calidad relacional. Una propuesta teórico-metodológica

[338] p.

The deliberate practice: the sports excellence versus the musical excellence

[ENG] If we look around us, we can observe that there is someone who is the best in each field of activity. We could think that they are exceptional individuals. This Final Project aims to increase knowledge of the effects of Deliberate Practice in the domains of music and sport. This will define you a concept of Deliberate Practice and then focus on the diversity of situations in which it shows us how it is presented in real life. From a questionnaire that has been designed for this study and distributed to the music students, I have expected to obtain a result that allow me to come to the conclusion that exists a relation between the hours of practice and the expertise in the execution. This reality has been linked to the regarding situation in the sport practice, whose information has been provided by the coordinators of the different sports. Taking into account the limited number of references available, this work has focused on a qualitative analysis of the data, interpreted from my point of view and my personal experience, which has been confirmed in the results obtained. The statistics managed allow me to conclude that, although the argument is not definitive, the guide effort through deliberate practice is essential to achieve the excellence.

Evaluating boundary dependent errors in QM/MM simulations.

Hybrid quantum mechanics/molecular mechanics (QM/MM) simulations provide a powerful tool for studying chemical reactions, especially in complex biochemical systems. In most works to date, the quantum region is kept fixed throughout the simulation and is defined in an ad hoc way based on chemical intuition and available computational resources. The simulation errors associated with a given choice of the quantum region are, however, rarely assessed in a systematic manner. Here we study the dependence of two relevant quantities on the QM region size: the force error at the center of the QM region and the free energy of a proton transfer reaction. Taking lysozyme as our model system, we find that in an apolar region the average force error rapidly decreases with increasing QM region size. In contrast, the average force error at the polar active site is considerably higher, exhibits large oscillations and decreases more slowly, and may not fall below acceptable limits even for a quantum region radius of 9.0 A. Although computation of free energies could only be afforded until 6.0 A, results were found to change considerably within these limits. These errors demonstrate that the results of QM/MM calculations are heavily affected by the definition of the QM region (not only its size), and a convergence test is proposed to be a part of setting up QM/MM simulations.

In Bello, Pax: a responsabilidade penal dos brasileiros em Operações de Paz

Esta Tese analisa a possibilidade de responsabilização penal dos brasileiros que têm participado de operações de paz capitaneadas ou delegadas pela Organização das Nações Unidas. Além de apresentar como se procede esta responsabilização no ambiente nacional, também analisa a possibilidade de sua responsabilização internacional diante da evolução que esta tem constatado desde o final do período conhecido como guerra-fria. Para tanto, parte de uma contextualização histórica da evolução e modificação das operações de paz, mostrando como o Brasil também modificou sua inserção nesta questão, em especial depois de 1990. Decorrente desse relevante aumento de responsabilidades e numérico de brasileiros engajados nestas operações apresenta como a fundamentação doutrinária legal e normativa também sofreu significativas mudanças nas últimas décadas. A partir deste ponto, fazendo uso de metodologia analítico-descritiva, apresenta as qualificações jurídicas admitidas, análise dos principais documentos internacionais que abordam a responsabilização penal dos integrantes de operações de paz e como se processa a relação entre estes documentos e o ordenamento jurídico brasileiro. Procura analisar como se processa, no ambiente interno, a jurisdição e competência para julgamento destas questões. Apresenta como o direito internacional tem sido influenciado pelo crescimento do direito internacional penal e como este pode se manifestar diante de integrantes de operações de paz, fazendo, inclusive, uma abordagem de como outras cortes internacionais têm se manifestado sobre a questão. Parte de decisões de direito interno de outros países, mostra a contribuição que os tribunais Ad Hoc instituídos pela ONU trouxeram para culminar na análise da possibilidade (ou não) de responsabilização destes integrantes pelo Tribunal Penal Internacional, ou mesmo, por terceiros Estados fazendo uso da Jurisdição Universal. Assim, a tese demonstra que efetivamente o Brasil dispõe de meios para exercer sua plena jurisdição perante seus nacionais envolvidos nestas operações internacionais, no entanto, a fim de garantir maior adensamento de juridicidade e sustentação legal, aponta possíveis soluções como contribuição para dirimir eventuais ponderações internas e internacionais.