Asymmetric aminocatalysis: a modern strategy for molecules, challenges and life

The studies conducted during my Phd thesis were focused on two different directions: 1. In one case we tried to face some long standing problems of the asymmetric aminocatalysis as the activation of encumbered carbonyl compounds and the control of the diastereoisomeric ratio in the diastero- and enantioselective construction of all carbon substituted quaternary stereocenters adjacent a tertiary one. In this section (Challenges) was described the asymmetric aziridination of ,-unsaturated ketones, the activation of ,-unsaturated -branched aldehydes and the Michael addition of oxindoles to enals and enones. For the activation via iminium ion formation of sterically demanding substrates, as ,-unsaturated ketones and ,-unsaturated -branched aldehydes, we exploited a chiral primary amine in order to overcome the problem of the iminium ion formation between the catalyst and encumbered carbonylic componds. For the control of diastereoisomeric ratio in the diastero- and enantioselective construction of all carbon substituted quaternary stereocenters adjacent a tertiary one we envisaged that a suitable strategy was the Michael addition to 3 substituted oxindoles to enals activated via LUMO-lowering catalysis. In this synthetic protocol we designed a new bifunctional catalyst with an amine moiety for activate the aldehyde and a tioureidic fragment for direct the approach of the oxindole. This part of the thesis (Challenges) could be considered pure basic research, where the solution of the synthetic problem was the goal itself of the research. 2. In the other hand (Molecules) we applied our knowledge about the carbonylic compounds activation and about cascade reaction to the synthesis of three new classes of spirooxindole in enantiopure form. The construction of libraries of these bioactive compounds represented a scientific bridge between medicinal chemistry or biology and the asymmetric catalysis.

Advanced Mission Synthesis Algorithms for Vibration-based Accelerated Life-testing

In the field of vibration qualification testing, with the popular Random Control mode of shakers, the specimen is excited by random vibrations typically set in the form of a Power Spectral Density (PSD). The corresponding signals are stationary and Gaussian, i.e. featuring a normal distribution. Conversely, real-life excitations are frequently non-Gaussian, exhibiting high peaks and/or burst signals and/or deterministic harmonic components. The so-called kurtosis is a parameter often used to statistically describe the occurrence and significance of high peak values in a random process. Since the similarity between test input profiles and real-life excitations is fundamental for qualification test reliability, some methods of kurtosis-control can be implemented to synthesize realistic (non-Gaussian) input signals. Durability tests are performed to check the resistance of a component to vibration-based fatigue damage. A procedure to synthesize test excitations which starts from measured data and preserves both the damage potential and the characteristics of the reference signals is desirable. The Fatigue Damage Spectrum (FDS) is generally used to quantify the fatigue damage potential associated with the excitation. The signal synthesized for accelerated durability tests (i.e. with a limited duration) must feature the same FDS as the reference vibration computed for the component’s expected lifetime. Current standard procedures are efficient in synthesizing signals in the form of a PSD, but prove inaccurate if reference data are non-Gaussian. This work presents novel algorithms for the synthesis of accelerated durability test profiles with prescribed FDS and a non-Gaussian distribution. An experimental campaign is conducted to validate the algorithms, by testing their accuracy, robustness, and practical effectiveness. Moreover, an original procedure is proposed for the estimation of the fatigue damage potential, aiming to minimize the computational time. The research is thus supposed to improve both the effectiveness and the efficiency of excitation profile synthesis for accelerated durability tests.