Cocristalli di acidi dicarbossilici: sintesi, caratterizzazione e stabilità allo stato solido

It is well-known that crystalline materials obtain their fundamental physical properties from the molecular arrangement within the solid, and altering the placement and or interactions between these molecules can impact the properties of the particular solid. Solid state chemistry looks at an attempt to alter the chemical and physical solid-state properties of APIs through many different strategies as the formation of salts, polymorphs, hydrates, solvates, and cocrystals. The final aim of this work is to study the chemical and physical propriety of new crystal structures. The work consists of three parts. The first is the cocrystallization of α,ω-alkanedicarboxylics acids with pirimidine. Single-crystal X-ray diffraction analysis of this adduct have been carried out at RT, 150 and 200 K. The cocrystals show an alteration of their melting point similar to pure acids. The two significant deviations are for the cocrystals with succinico and glutarico acids. The second object of work is the structure determination of β polymorph undecandioic acids. In literature is known the other polymorph α. We observed that the thermodynamic relation for this dimorphics system is monotropic. In the third part we synthesized and analyzed the stability of four new salts of serine and oxalic acid. This project highlights the advantage of the solid state synthesis.

Design e sintesi di nuove sonde luminescenti per il "targeting" dell'avidina

Recent studies on the use of bio-conjugating organometallic probes report on the possibility to use biotinylated-derivatives to selectively coordinate to a specific protein, avidin. In the present thesis, the synthesis of four new bifunctional ligands is described. The ligands contain both a pyridine triazolic unit able to coordinate a transition metal, and a biotin fragment able to bond avidin: the two functionalities are linked together by an appropriate aromatic linker (amide or ester). The obtained ligands were then employed to form luminescent Ir(III) complexes, that have been fully characterized also by a photophysical point of view both in organic and in aqueous solvent. Therefore, titrations of solutions of avidin with aqueous solutions of Ir(III)-complexes have been performed in order to estimate the luminescence variations of the complexes in the presence or in the absence of bio-conjugation.

Studies towards the total synthesis of penicillipyrone b via a biomimetic approach

Pennicillipyrone A and B are two novel meroterpenoids isolated from the marine-derived fungus Penicilliump sp. Although a preliminary toxicity studies demonstrated the bioactivity of penicillipyrone A to be far superior to that of its congener penicillipyrone B, we were intrigued by its structure. Moreover, it appeared as though one could design an efficient total synthesis based on chemistry that was familiar to our laboratory. The purpose of this project was the study of a new synthesis of Pennicillipyrone B by way of a doubley-biomimetic approach. The intended approach proceeds through a polyene cascade reaction terminated by a nucleophilic pyrone - a reaction not yet known in the literature for the construction of this type of scaffold. During the course of this study we have learned about the unanticipated reactivity of C2 substituted keto-dioxinones with regard to self-condensation. In addition, four new compounds were synthesized and two synthetic routes to the target molecule are presented.