A DFT study on chemodivergent preparation of piperidinic and morpholinic heterocycles

The topic of this thesis is the DFT computational study of the mechanisms for the synthesis of chiral 3,4,5-trisubstituted piperidines and 2,6-disubstituted morpholines. The goal of this synthesis is to use, the same substrate containing two electrophilic sites: an α,β-unsaturated ester and a ketone, which evolve according to the nucleophile used (cyanide, phenyl sulfide) through different addition and cyclization reactions. A quaternary ammonium salt is used as a catalyst for these reactions, which leads to a diastereoisomeric excess both for the reactions of morpholine and piperidine products. Studies in silico of the pathways of these reactions explain the chemoselection and diasteroselection deriving from the two nucleophiles used. In this case of piperidine products, it was also possible to validate the hypothesis of a concerted nucleophilic addition mechanism on the α,β-unsaturated site and cyclization due to an intramolecular Michael addition.

Preparation and Characterization of Polymeric Beads and Membranes for Boron Removal From Water

Boron is an element essential for various biological processes, nevertheless at high concentration it can cause health issues in both plants and animals, thus making boron a pollutant element. Low cost and effective polymeric adsorbents capable of removing boron in aqueous solution at neutral pH were prepared for this purpose. The adsorbent selectivity towards boron was conferred taking advantage of the interaction between boric acid and the alcoholic groups of N-methyl-D-Glucamine, which are able to form specific complexes. Two different kinds of devices were produced and tested: cross-linked chitosan hydrogel beads (CCBMG) and PVA/chitosan membranes, the latter taking advantage of scCO2-assisted phase inversion technique. The capability of the adsorbents to be regenerated and to allow recovery of boric acid from a solution emulating the concentration of boric acid in seawater were evaluated.

Root cause analysis applied to a finite element model's refinement of a negative stiffness structure

Negative Stiffness Structures are mechanical systems that require a decrease in the applied force to generate an increase in displacement. They are structures that possess special characteristics such as snap-through and bi-stability. All of these features make them particularly suitable for different applications, such as shock-absorption, vibration isolation and damping. From this point of view, they have risen awareness of their characteristics and, in order to match them to the application needed, a numerical simulation is of great interest. In this regard, this thesis is a continuation of previous studies in a circular negative stiffness structure and aims at refine the numerical model by presenting a new solution. To that end, an investigation procedure is needed. Amongst all of the methods available, root cause analysis was the chosen one to perform the investigation since it provides a clear view of the problem under analysis and a categorization of all the causes behind it. As a result of the cause-effect analysis, the main causes that have influence on the numerical results were obtained. Once all of the causes were listed, solutions to them were proposed and it led to a new numerical model. The numerical model proposed was of nonlinear type of analysis with hexagonal elements and a hyperelastic material model. The results were analyzed through force-displacement curves, allowing for the visualization of the structure’s energy recovery. When compared to the results obtained from the experimental part, it is evident that the trend is similar and the negative stiffness behaviour is present.