Synthesis and characterization of hydroxyapatite modified with (9r)-9-hydroxystearic acid

(9R)-9-hydroxystearic acid (9R-HSA) has been proven to have antitumoral activity because it is shown to inhibit histone deacetylase 1, an enzyme which activates DNA replication, and the (R)-enantiomer has been shown to be more active than the (S)-enantiomer both in vitro and by molecular docking. Hydroxyapatite is the main mineral component of bone and teeth and has been used for over 20 years in prostheses and their coating because it is biocompatible and bioactive. The goal of incorporating 9R-HSA into hydroxyapatite is to have a material that combines the bioactivity of HA with the antitumoral properties of 9R-HSA. In this work, 9R-HSA and its potassium salt were synthesized and the latter was also incorporated into hydroxyapatite. The content of (R)-9-hydroxystearate ion incorporated into the apatitic structure was shown to be a function of its concentration in solution and can reach values higher than 8.5%. (9R)-9-hydroxystearic acid modified hydroxyapatite was extensively characterized to determine the effect of the incorporation of the organic molecule. This incorporation does not significantly alter the unit cell but reduces the size of both the crystals as well as the coherent domains, mainly along the a-axis of hydroxyapatite. This is believed to be due to the coordination of the negatively charged carboxylate group to the calcium ions which are more exposed on the (100) face of the crystal, therefore limiting the growth mainly in this direction. Further analyses showed that the material becomes hydrophobic and more negatively charged with the addition of 9R-HSA but both of these properties reach a plateau at less than 5% wt of 9R-HSA.

Synthesis, Characterization and Conformational Studies of Modified Carbazole-bis-aryl-boranes

During this project we have synthetized different compounds belonging to the class of amino-boranes for the study of bis-aryl-B=N system. We have decided to keep unchanged the aryl components and change only the amine to observe the effect of that on the B=N bond. The used amines are modified carbazoles with functional groups chosen to amplify or disempower the steric and the conjugation effect. We have found that the evaluation of steric barrier was possible studying the gearing aryls rotation around the C-B bonds, while the conjugation barrier is instead given by the energy needed to break the formal double bond B=N and allow the amine rotation. The work started with a proposed synthesis, improved for every reaction, then the products are characterized by NMR, fluorometric spectroscopy, mass spectrometry and X-Ray diffraction on single crystal. The following study on rotational energy barrier was possible theoretically through DFT calculation and experimentally with techniques like Dynamic NMR and EXSY. The fluorometric analysis was done for the study of the solvatochromic propriety of the products.

Modelling the Halo mass number counts in modified gravity cosmological scenarios

In this Thesis work we investigate some of different cosmological background scenarios using one of the main probes used in cosmology: the halo mass function. The observed abundance of galaxy clusters (or similarly DM haloes) can indeed be compared to its theoretical predictions to derive fundamental constrains on the cosmological scenario assumed. Given the importance of exploring and constraining models degenerate with the ΛCDM one, we test the applicability of some notable halo mass function models to these scenarios. To this purpose, we made use of the DUSTGRAIN-pathfinder N-body simulations, which assume cosmological scenarios that include modified gravity in the form of f(R) models and massive neutrinos. We carried on the analysis of 3 simulation snapshots at different redshifts, z = 0, 0.5, 1, building multiple samples of dark matter haloes by applying different overdensity thresholds during the procedure of halo identification. We started our analysis by considering the halo mass function model introduced by Despali et al. (2016), who proposed a parametrization that encapsulates the effect of the different halo mass definitions and the relative evolution with the redshift. We calibrated the main parameters of this relation by using the ΛCDM halo catalogues extracted from the DUSTGRAIN-pathfinder simulations, fitting the measured halo abundances at all redshifts and density thresholds. Afterwards we tested the same model parametrization with halo catalogues extracted from the simulations implementing both modified gravity and massive neutrinos. We repeated therefore the calibration procedure on these data to search for discrepancies with respect to the ΛCDM model. Finally we focused the analysis on the cosmological models implementing modified gravity only. We took our ΛCDM calibrated halo mass function and we modified it with the additional f (R) gravity form proposed by Gupta et al. (2022).