The structure of nano sized poorly-crystalline iron oxy-hydroxides

In this thesis the structures of three nano sized poorly-crystalline iron oxy-hydroxides, feroxyhyte, ferrihydrite and schwertmannite, are studied and analyzed with the aim of clarifying some dubious structural features. The widely used Rietveld re�nement and EXAFS analysis are employed in order to address the consistency of the structural models proposed for these materials, one of which, feroxyhyte, is suggested in this thesis. Furthermore, a new computer program exploiting the Reverse Monte Carlo algorithm and the Debye Scattering Equation is presented and used in order to analyze the elusive structures of these iron oxy-hydroxides.

Theranostic applications of fluorescent liquid crystalline nanoparticles

Lipid liquid crystalline nanoparticles can find application as nanocarriers in several fields of the daily life but, very likely, the pharmaceutical arena is the most relevant. Indeed, several problems encountered in drugs administration (e.g. critical sideeffects from antitumor drugs) require alternative, less invasive, but simultaneously efficient therapeutic routes to be explored. Novel fields of personalized nanomedicine are developing in this direction. One of the most interesting is theranostic, which calls for the design of platforms capable of combining therapeutic and diagnostic functionalities. In this optic, we explored the potential of monoolein-based cubosomes and hexosomes as nanocarriers for theranostic purposes. Our work focussed on the design of lipid nanoparticles able to deliver antineoplastic drugs and imaging probes for fluorescent optical in vitro and in vivo imaging. We developed cubosome formulations loaded with antineoplastic drugs and useful for the fluorescence imaging of cells. Such formulations were also actively targeted to cancer cells and coupled with a NIR-emitting fluorophore, which was the promise for in vivo applications. We also investigated hexosomes with encouraging results encapsulating in their lipid matrix a BODIPY derivative with solvatochromic properties, helpful for the understanding of the dye localization. Importantly, we reported (manuscript submitted) the first proof-of-principle for in vivo fluorescence optical imaging application using monoolein-based cubosomes in a healthy mouse animal model. Finally, since relatively little is known about the interaction of cubosomes with biological systems, their effects on lipid droplets, mitochondria and lipid profile of HeLa cells were deeply studied. This thesis is divided in two main parts. The introduction section reports on the essential background of the research field, and it is followed by the publications (published or submitted) resulting from these three years of work.

Efects of mineral suspension and dissolution on strength and compressibility of soft carbonate rocks

© 2014 Elsevier B.V.Calcarenites are highly porous soft rocks formed of mainly carbonate grains bonded together by calcite bridges. The above characteristics make them prone to water-induced weathering, frequently featuring large caverns and inland natural underground cavities. This study is aimed to determine the main physical processes at the base of the short- and long-term weakening experienced by these rocks when interacting with water. We present the results of microscale experimental investigations performed on calcarenites from four different sites in Southern Italy. SEM, thin sections, X-ray CT observations and related analyses are used for both the interpretation-definition of the structure changes, and the identification-quantification of the degradation mechanisms. Two distinct types of bonding have been identified within the rock: temporary bonding (TB) and persistent bonding (PB). The diverse mechanisms linked to these two types of bonding explain both the observed fast decrease in rock strength when water fills the pores (short-term effect of water), identified with a short-term debonding (STD), and a long-term weakening of the material, when the latter is persistently kept in water-saturated conditions (long-term effect of water), identified with a long-term debonding (LTD). To highlight the micro-hydro-chemo-mechanical processes of formation and annihilation of the TB bonds and their role in the evolution of the mechanical strength of the material, mechanical tests on samples prepared by drying partially saturated calcarenite powder, or a mix of glass ballotini and calcarenite powder were conducted. The long-term debonding processes have also been investigated, using acid solutions in order to accelerate the reaction rates. This paper attempts to identify and quantify differences between the two types of bonds and the relative micro-scale debonding processes leading to the macro-scale material weakening mechanisms.

Low temperature X-ray structures of two crystalline forms (I) and (II) of the pyrimidine derivative and sodium channel blocker BW1003C87: 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine

The X-ray crystal structures of two crystalline forms of 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine, C10H7Cl3N4 (code name BW1003C87) (I) and (II), have been carried out at liquid nitrogen temperature. A detailed comparison of the two structures is given. Both are centrosymmetric, with structure (I) in the triclinic space group P (1) over bar unit cell a = 6.4870(10), b = 9.216(2), c = 12.016(2) angstrom, alpha = 75.78(3)degrees, beta = 89.95(3)degrees, gamma = 83.45(3)degrees, V = 691.5(2) angstrom(3), Z = 2 and density (calculated) = 1.544 Mg/m(3); and (II) in the monoclinic space group P2(1)/c, unit cell a = 12.000(2), b = 7.518(2), c = 13.450(3) angstrom, beta = 97.87(3)degrees, V = 1202.0(5) angstrom(3), Z = 4, Density (calculated) = 1.600 Mg/m(3). Structure (I) includes a solvated CH3OH in the lattice. Final R indices [I > 2sigma(I)] are R1 = 0.0427, wR2 = 0.1075 for (I) and R1 = 0.0487, wR2 = 0.1222 for (II). R indices (all data) are R1 = 0.0470, wR2 = 0.1118 for (I) and R1 = 0.0623, wR2 = 0.1299 for (II). 5-Phenyl-2,4 diaminopyrimidine and 6-phenyl-1,2,4 triazine derivatives, which include lamotrigine (3,5-diamino-6-(2,3-dichlorophenyl)-1,2,4-triazine), have been investigated for some time for their effects on the central nervous system. Both lamotrigine and 5-(2,3,5-trichlorophenyl)-2,4-diaminopyrimidine (code name BW1003C87), the subject of the present study, are anticonvulsant as well as neuroprotective in models of brain ischaemia and in a model of white matter ischaemia. BW1003C87 is a sodium channel blocker which also reduces the release of the neurotransmitter glutamate. The three dimensional structures reported here form part of a newly developed data base for the detailed investigation of members of this drug family and their biological activities.