NMR Spectroscopic Investigations on Asymmetric Aminocatalysis

In this thesis, the main focus of interest was the generation of an improved understanding about reaction mechanisms in modern organic chemistry by NMR spectroscopy. For the first time, several mechanistic questions in asymmetric aminocatalysis, including enamine and dienamine catalysis were answered by using a powerful combination of new tools and techniques (CEST, RDS-shift) with well-established NMR spectroscopic methods, like coupling constant analysis and 2D experiments. Additionally, to further push the boundaries of the field of reaction mechanism analysis, the application of the recently published DTS-hv method for the analysis of reaction pathways was transferred to the field of iminium ion catalysis and an innovative UVNMR-illumination setup was developed

Church of Saint Joseph of Anchieta-Pateo do Collegio: The renovation of places of worship

Pateo do Collegio es el lugar donde se fundó São Paulo en 1554. Los primeros edificios —una universidad y una iglesia— presentaban arquitectura colonial en el siglo XVII, y la iglesia en el siglo XVIII fue abandonada después de la expulsión de los jesuitas del país. Demolido a fines del siglo XIX, a principios del siglo XX fue nuevamente propiedad de los jesuitas y se construyó un nuevo edificio. En 2009 hubo una importante renovación de sus lugares de culto, realizada por Claudio Pastro. La disposición de los elementos es inusual y, sin embargo, conveniente. Pastro materializó la influencia del Concilio Vaticano II en el arte y la arquitectura, siendo una de las voces autorizadas en Brasil que fomentó experiencias paradigmáticas. El estudio de esta reforma es el objeto de este artículo: analizar el proyecto elaborado y ejecutado, identificar las soluciones proyectuales y registrar con rigor la contribución de esta arquitectura contemporánea.Pateo do Collegio is the place where São Paulo was founded in 1554. The first buildings —a college and a church— featured colonial architecture in the 17th century, and the church in the 18th was abandoned after expulsion of the Jesuits from the country. Demolished in the late nineteenth century, in the early twentieth it was again owned by the Jesuits and a new building was built. In 2009 there was an important renovation of their places of worship, by Claudio Pastro. The arrangement of the elements is unusual and yet convenient. Pastro materialized the influence of the Second Vatican Council on art and architecture, being one of the authorized voices in Brazil that fostered paradigmatic experiences. The study of this reform is the object of this article: to analyze the elaborated and executed project, to identify the projectual solutions and to accurately record the contribution of this contemporary architecture

Forma, estructura y simbolismo: Un proyecto moderno para la Iglesia Nacional Presbiteriana de Brasilia

In 1964, a national project contest was organized for the Presbyterian National Church in the newly opened capital of Brazil, Brasilia. The winning project, carried out by the architects Ubirajara Motta Lima Ribeiro and Sergio A.B. Machado presents excellent architectural qualities, inventive composition and an intelligent rationalization of the constructive solution. If it had been built, it would undoubtedly be a masterpiece. The simplicity of the results is based on a limited range of constructive elements, which, however, could bring significant complexity to the architectural spaces, whose design adequately meets the symbolic load of a congregational and sacred space. This article intends to study this modern project a little more, digitally recovering its design and suggesting possible architectural and theoretical interpretations considering the different scales, from the urban condition to the details and tectonic aspects.En 1964 se organizó un concurso nacional de proyectos para la Iglesia Nacional Presbiteriana en la recién inaugurada capital de Brasil, Brasilia. El proyecto ganador, realizado por los arquitectos Ubirajara Motta Lima Ribeiro y Sergio A.B. Machado, presenta excelentes cualidades arquitectónicas, inventiva composición y una inteligente racionalización de la solución constructiva. Si se hubiera construido sería, sin duda, una obra maestra. La simplicidad de resultados se apoya en una gama limitada de elementos constructivos, que sin embargo llegarían a aportar una relevante complejidad a los espacios arquitectónicos, cuyo diseño atiende adecuadamente a la carga simbólica de un espacio congregacional y sagrado. Este articulo se propone estudiar un poco más ese proyecto moderno, recuperando digitalmente su diseño y sugiriendo posibles interpretaciones arquitectónicas y teóricas considerando las diversas escalas, desde la condición urbana a los detalles y aspectos tectónicos

Forma e iconografía en las iglesias católicas de Oriente: Los ejemplos en las dos últimas ediciones del Premio Internazionale di Architettura Sacra Frate Sole

The International Prize for Sacred Architecture granted by the Frate Sole Foundation, for twenty-five years, makes it possible to monitor the state of the art regarding contemporary religious architecture. Its seven editions offer an unbeatable architectonic panorama for the Christian confessional destiny. Focusing on Catholic architecture in the Far East, the work proposes to analyze the works submitted in the last two editions, and to identify project decisions on architecture and iconography. In this way, the formal expressions and built materials will be observed, the relationship between temple and nature, and an attempt will be made to recognize in the images the acting influences, Western or specifically Eastern. The participating production of the award is a catalog for the study of temples and their conception, capable of nourishing these and other observations.El Premio Internacional de Arquitectura Sacra otorgado por la Fundación Frate Sole desde hace veinticinco años, permite monitorear el estado del arte respecto de la arquitectura religiosa contemporánea. Sus siete ediciones brindan un inmejorable panorama de obra construida con destino confesional cristiano. Haciendo foco en la arquitectura católica en Extremo Oriente, el trabajo propone analizar las obras postuladas en las dos últimas ediciones, e identificar decisiones proyectuales sobre la arquitectura e iconografía. De este modo se observarán las expresiones formales y materiales construidas, la relación entre templo y naturaleza, y se intentará reconocer en las imágenes las influencias actuantes, occidentales o propiamente orientales. La producción participante del galardón es un catálogo para el estudio de templos y su concepción, capaz de nutrir éstas y otras observaciones

Pruning by Explaining: A Novel Criterion for Deep Neural Network Pruning

The success of convolutional neural networks (CNNs) in various applications is accompanied by a significant increase in computation and parameter storage costs. Recent efforts to reduce these overheads involve pruning and compressing the weights of various layers while at the same time aiming to not sacrifice performance. In this paper, we propose a novel criterion for CNN pruning inspired by neural network interpretability: The most relevant units, i.e. weights or filters, are automatically found using their relevance scores obtained from concepts of explainable AI (XAI). By exploring this idea, we connect the lines of interpretability and model compression research. We show that our proposed method can efficiently prune CNN models in transfer-learning setups in which networks pre-trained on large corpora are adapted to specialized tasks. The method is evaluated on a broad range of computer vision datasets. Notably, our novel criterion is not only competitive or better compared to state-of-the-art pruning criteria when successive retraining is performed, but clearly outperforms these previous criteria in the resource-constrained application scenario in which the data of the task to be transferred to is very scarce and one chooses to refrain from fine-tuning. Our method is able to compress the model iteratively while maintaining or even improving accuracy. At the same time, it has a computational cost in the order of gradient computation and is comparatively simple to apply without the need for tuning hyperparameters for pruning.Comment: 25 pages + 5 supplementary pages, 13 figures, 6 table

Machine learning models predict the primary sites of head and neck squamous cell carcinoma metastases based on DNA methylation

In head and neck squamous cell cancers (HNSCs) that present as metastases with an unknown primary (HNSC-CUPs), the identification of a primary tumor improves therapy options and increases patient survival. However, the currently available diagnostic methods are laborious and do not offer a sufficient detection rate. Predictive machine learning models based on DNA methylation profiles have recently emerged as a promising technique for tumor classification. We applied this technique to HNSC to develop a tool that can improve the diagnostic work-up for HNSC-CUPs. On a reference cohort of 405 primary HNSC samples, we developed four classifiers based on different machine learning models [random forest (RF), neural network (NN), elastic net penalized logistic regression (LOGREG), and support vector machine (SVM)] that predict the primary site of HNSC tumors from their DNA methylation profile. The classifiers achieved high classification accuracies (RF = 83%, NN = 88%, LOGREG = SVM = 89%) on an independent cohort of 64 HNSC metastases. Further, the NN, LOGREG, and SVM models significantly outperformed p16 status as a marker for an origin in the oropharynx. In conclusion, the DNA methylation profiles of HNSC metastases are characteristic for their primary sites, and the classifiers developed in this study, which are made available to the scientific community, can provide valuable information to guide the diagnostic work-up of HNSC-CUP. (c) 2021 The Authors. The Journal of Pathology published by John Wiley & Sons Ltd on behalf of The Pathological Society of Great Britain and Ireland

Symbolic Task Compression in Structured Task Learning

Learning everyday tasks from human demonstrations requires unsupervised segmentation of seamless demonstrations, which may result in highly fragmented and widely spread symbolic representations. Since the time needed to plan the task depends on the amount of possible behaviors, it is preferable to keep the number of behaviors as low as possible. In this work, we present an approach to simplify the symbolic representation of a learned task which leads to a reduction of the number of possible behaviors. The simplification is achieved by merging sequential behaviors, i.e. behaviors which are logically sequential and act on the same object. Assuming that the task at hand is encoded in a rooted tree, the approach traverses the tree searching for sequential nodes (behaviors) to merge. Using simple rules to assign pre- and post-conditions to each node, our approach significantly reduces the number of nodes, while keeping unaltered the task flexibility and avoiding perceptual aliasing. Experiments on automatically generated and learned tasks show a significant reduction of the planning time