OpenDataHub: an open dataset management system

This thesis presents a cloud-based software platform for sharing publicly available scientific datasets. The proposed platform leverages the potential of NoSQL databases and asynchronous IO technologies, such as Node.JS, in order to achieve high performances and flexible solutions. This solution will serve two main groups of users. The dataset providers, which are the researchers responsible for sharing and maintaining datasets, and the dataset users, that are those who desire to access the public data. To the former are given tools to easily publish and maintain large volumes of data, whereas the later are given tools to enable the preview and creation of subsets of the original data through the introduction of filter and aggregation operations. The choice of NoSQL over more traditional RDDMS emerged from and extended benchmark between relational databases (MySQL) and NoSQL (MongoDB) that is also presented in this thesis. The obtained results come to confirm the theoretical guarantees that NoSQL databases are more suitable for the kind of data that our system users will be handling, i. e., non-homogeneous data structures that can grow really fast. It is envisioned that a platform like this can lead the way to a new era of scientific data sharing where researchers are able to easily share and access all kinds of datasets, and even in more advanced scenarios be presented with recommended datasets and already existing research results on top of those recommendations.

New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.