Estudo teórico sobre o efeito de substituintes na estrutura eletrônica de supermoléculas com múltiplas ligações de hidrogênio intermoleculares

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro de Ciências Físicas e Matemáticas, Programa de Pós-Graduação em Química, Florianópolis, 2013Sistemas que se conectam através de múltiplas ligações de hidrogênio são a pedra angular dos processos de reconhecimento molecular e estão cada vez mais sendo empregados em processos de auto-montagem molecular. Sendo assim, optou-se por conduzir uma investigação dos efeitos causados por substituintes na estrutura eletrônica e na magnitude das ligações de hidrogênio intermoleculares em sistemas tipo AAA-DDD. Os efeitos dos substituintes foram investigados empregando-se duas análises topológicas, a Função de Localização de Elétrons e a Teoria Quântica dos Átomos em Moléculas (ELF e QTAIM, respectivamente), e duas análises energéticas, uma baseada na decomposição da energia de interação intermolecular, Su-Li EDA, e a outra no formalismo dos Orbitais Naturais de Ligação, NBO. Os resultados baseados QTAIM e ELF e NBO indicam que a presença de substituintes com grande poder retirador de elétrons aumentam o grau de covalência das interações intermolecular nos sistemas analisados, enquanto que substituintes doadores de elétrons tendem a diminuí-lo. Os resultados Su-Li EDA reforçam essas evidências e fornecem ainda um perfil quantitativo da influência dos diferentes grupos substituintes e da posição de substituição nas energia de interação intermolecular. Foi constatado que para os sistemas estudados, a influência dos substituintes na força das ligações de hidrogênio é apenas moderado.Abstract : Systems that connect via multiple hydrogen bonds are the cornerstone of molecular recognition processes in biology and are increasingly being employed in supramolecular chemistry, specifically in processes of molecular self-assembly. In this scenario, it was decided to carry out an investigation of the effects caused by different substituents on the electronic structure and thus on the magnitude of the intermolecular hydrogen bonds in AAA-DDD systems. The effects of substituents were investigated by employing two topological analyses, the Electron Localization Function of and Quantum Theory of Atoms in Molecules (ELF and QTAIM, respectively), and two energetic analyses, one based on the decomposition of intermolecular interaction energy, Su-Li EDA, and the other on the formalism of Natural Bonding Orbitals, NBO. The evaluation of variations in geometric parameters of hydrogen bonds caused by the substitution was also performed. The results based on hydrogen bond local descriptors (geometry, QTAIM and ELF) indicate that the presence of electron withdrawing substituents increases the degree of covalency of the intermolecular interactions for the analyzed systems, while electron donating substituents tend to decrease it. The strength of the intermolecular hydrogen bonds proved to be dependent on both nature and the position of the substituent group. The results of the energy decomposition analysis, Su-Li EDA, reinforce these evidences and also provide a quantitative profile of the influence of different substituents and the position of substitution on intermolecular interaction energy. It was found that for the systems under study, the influence of substituents on the strength of hydrogen bonds is only moderate

La comunicación participativa vista y aplicada desde la Corporación Mujeres Conquistadoras y Productivas en la Localidad de Usme, Puerta al llano.

A través del siguiente ensayo crítico se examina, se observa y se evidencia como es el manejo adecuado que existe en la Corporación Mujeres Conquistadoras y Productivas, en relación con la comunicación participativa sea interna y externa con la comunidad versus con la corporación, la cual se desarrollará en una transformación limpia y transparente. Todo el proceso argumentativo y análisis estará apoyado por los distintos planteamientos de los autores trabajados en el DCRSC. Se busca y se pretende que el lector comprenda la importancia del amor, la solidaridad e igualdad entre todos para fortalecer las bases sociales y de esta manera poder generar una comunicación participativa transparente dentro y fuera de la organización. Este ensayo es resultado de una investigación acción de tipo socio praxis, que duró tres meses aproximadamente, realizada con el fin de la opción de grado de la carrera, por medio de este diplomado “Construcción de Redes Sociales en Comunicación”, seré una futura Comunicadora Social.Through the following critical essay, the proper management that exists in the Corporación Mujeres Conquistadoras y Productivas is examined, observed and evidenced, in relation to participatory communication, both internal and external with the community versus with the corporation, which is will develop into a clean and transparent transformation. The entire argumentative process and analysis will be supported by the different approaches of the authors worked in the DCRSC. It is sought and is intended that the reader understands the importance of love, solidarity and equality among all to strengthen the social bases and thus be able to generate a transparent participatory communication inside and outside the organization. This essay is the result of a socio-praxis-type action investigation, which lasted approximately three months, carried out with the aim of the degree option of the career, through this diploma "Construction of Social Networks in Communication", I will be a future Communicator Social

Hotel Factory Corferias

El proyecto para el diseño y puesta en marcha de un hotel con capacidad instalada de 52 habitaciones de ocupación doble y triple para un número de 112 huéspedes al día con ocupación plena. El Hotel Factory Corferias se caracterizará por ser un recinto acogedor, confortable y con un excelente servicio, atención personalizada, con personal capacitado y empoderado para dar solución a las necesidades de los huéspedes a la mayor brevedad posible e incluso dando más de aquello que puedan requerir, vendiendo la idea de tomar los planes turísticos acordes a sus preferencias y necesidades comerciales pero sobre todo a precios muy competitivos. Calidad, seguridad, confort y oferta de servicios que cubran los requerimientos de los empresarios serán nuestra ventaja competitiva, principalmente este último aspecto ya que ninguno de los hoteles del sector cuenta con este servicio.The project for the design and implementation of a hotel with installed capacity of 52 rooms triple double occupancy, for a total of 112 guests per day with full occupancy. The Hotel will feature Factory Corferias be a welcoming, comfortable and excellent service enclosure, personalized service, with trained and empowered to solve the needs of the guests as soon as possible and even giving more than what they can require , selling the idea of ​​taking the chords tourist plans to their preferences and business needs but above all, affordable. Quality, safety, comfort and service offerings that meet the requirements of employers will be our competitive advantage, the latter mainly because none of the sector hotels have this service.Magíster en Creación y Dirección de Empresas

Nanostructured heterogeneous catalysts for bioorthogonal reactions

Bioorthogonal chemistry has inspired a new subarea of chemistry providing a powerful tool to perform novel biocompatible chemospecific reactions in living systems. Following the premise that they do not interfere with biological functions, bioorthogonal reactions are increasingly applied in biomedical research, particularly with respect to genetic encoding systems, fluorogenic reactions for bioimaging, and cancer therapy. This Minireview compiles recent advances in the use of heterogeneous catalysts for bioorthogonal reactions. The synthetic strategies of Pd-, Au-, and Cu-based materials, their applicability in the activation of caged fluorophores and prodrugs, and the possibilities of using external stimuli to release therapeutic substances at a specific location in a diseased tissue are discussed. Finally, we highlight frontiers in the field, identifying challenges, and propose directions for future development in this emerging field.Agencia Estatal de Investigación | Ref. PID2020-113704RB-I00Xunta de Galicia | Ref. ED431C 2022/24Xunta de Galicia | Ref. ED431H 2020/08Xunta de Galicia | Ref. ED431G 2019-06Xunta de Galicia | Ref. ED481B-2019-07

Seasonal and spatial variability in plankton production and respiration in the Subtropical Gyres of the Atlantic Ocean

Euphotic zone plankton production (P) and respiration (R) were determined from the in vitro flux of dissolved oxygen during six latitudinal transects of the Atlantic Ocean, as part of the Atlantic Meridional Transect (AMT) programme. The transects traversed the North and South Atlantic Subtropical Gyres (N gyre, 18–38°N; S gyre, 11–35°S) in April–June and September–November 2003–2005. The route and timing of the cruises enabled the assessment of the seasonal variability of P, R and P/R in the N and S gyres, and the comparison of the previously unsampled N gyre centre with the more frequently sampled eastern edge of the gyre. Mean euphotic zone integrated rates (±SE) were P=63±23 (n=31), R=69±22 (n=30) mmol O2 m-2 d-1 in the N gyre; and P=58±26 (n=30), R=62±24 (n=30) mmol O2 m-2 d-1 in the S gyre. Overall, the N gyre was heterotrophic (R>P) and it was more heterotrophic than the S gyre, but the metabolic balance of both gyres changed with season. Both gyres were net heterotrophic in autumn, and balanced in spring. This seasonal contrast was most pronounced for the S gyre, because it was more autotrophic than the N gyre during spring. This may have arisen from differences in nitrate availability, because spring sampling in the S gyre coincided with periods of deep mixing to the nitracline, more frequently than spring sampling within the N gyre. Our results indicate that the N gyre is less heterotrophic than previous estimates suggested, and that there is an apparent decrease in R from the eastern edge to the centre of the N gyre, possibly indicative of an allochthonous organic carbon source to the east of the gyre

Probability model of bicycle accident. Case study Engativá, Bogotá

En Bogotá se ha incrementado el uso de la bicicleta y, con este, los índices en accidentalidad, ya que para el 2017 se presentó una cifra de 71 ciclistas muertos y 1.271 lesionados. A pesar de que existen campañas de seguridad vial, la cantidad de accidentes no disminuye. Con base en una revisión del estado del arte, en los últimos 5 años se observa que hay registros de la accidentalidad explicada de manera monocausal pero no un análisis integral de las diferentes causas en contexto. Se presenta una investigación descriptiva que desarrolla un modelo que explica qué variables influyen en la ocurrencia de un accidente en bicicleta,para lo cual se utilizó información histórica de accidentalidad, facilitada por la Secretaría de Movilidad de Bogotá de los años 2015 a 2018, con las causales de accidentalidad reportadas. Se identificaron variables de accidentalidad de investigaciones del tema a nivel mundial, regional y local. Se compararon con información de encuestas a 280 biciusuarios de la localidad de Engativá. Se obtiene un árbol de sucesos en que se asocian las variables y de cadauna de ellas, el cálculo de la probabilidad frecuentista del suceso, cuyo cálculo está sujeto a la existencia o no de un accidente en bicicleta. Se aplicó el teorema de Bayes para explicar las variables condicionadas e integradas.En conclusión, este modelo identifica las variables más significativas presentes en la accidentalidad en viaje en bicicleta, como base para orientar la formulación de campañas y políticas públicas más efectivas. In Bogotá, the use of the bicycle has increased and the rates of accidents have increased, with around 71 dead cyclists and 1271 injured by 2017. Despite the existence of road safety campaigns, the accident figures are not consistent. Based on a review of the state of the art, in the last 5 years it is observed that there are records of the accident explained in a mono-causal way but not an integral analysis of the different causes in context. This article presents a descriptive investigation that develops a model that explains which variables influence the occurrence of an accident on the bicycle trip, for which historical information was used of the accident of the Mobility Secretariat of Bogotá from 2015 to 2018, with the accident causes reported. Accident variables of investigations of the topic at the global, regional and local level were identified. They were compared with survey information to 520 bicycle user of the Town of Engativá.An Event tree is applied, associating with it the variables and of each of them the calculation of the frequentistic probability of the event, whose calculation is subject to the existence or not of an accident on the bicycle trip. Bayes theorem was applied to explain the conditioned and integrated variables.In conclusion, this model identifies the most significant variables present in the accident on a bicycle trip, as a basis to guide the formulation of more effective public campaigns and policies. Em Bogotá, o uso da bicicleta aumentou e, com ela, os índices de acidentes, já que em 2017 havia 71 ciclistas mortos e 1.271 feridos.  Embora existam campanhas de segurança rodoviária, o número de acidentes não diminui. Com base em uma revisão do estado da arte, nos últimos 5 anos, observa-se que há registros do acidente explicados de forma monocausal, mas não uma análise integral das diferentes causas no contexto. Este artigo apresenta uma investigação descritiva que desenvolve um modelo que explica quais variáveis influenciam a ocorrência de um acidente no passeio de bicicleta, para o qual foram utilizadas informações históricas do acidente, fornecidas pela Secretaria de Mobilidade de Bogotá de los anos de 2015 a 2018, com as causas do acidente relatadas. As variáveis de acidente foram identificadas para pesquisas sobre o tema em nível mundial, regional e local. Eles foram comparados cominformações de pesquisas a 280 biciusarios da localidade de Engativá. É aplicado para obter uma árvore de eventos alemães que associa as variáveis e a cada uma delas, o cálculo da probabilidade freqüencial do evento, cujo cálculo está sujeito à existência ou não de um acidente na viagem de bicicleta. O teorema de Bayes foi aplicado para explicar as variáveis condicionadas e integradas.Concluindo, este modelo identifica as variáveis mais significativas presentes no acidente em um passeio de bicicleta, como base para orientar a formulação de campanhas e políticas públicas mais eficazes.&nbsp