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Giordano M Di Gregorio

Publications and source records attributed to Giordano M Di Gregorio.

3 recordsLinked to original sources

Rigidity and spontaneous curvature of lipidic monolayers in the presence of trehalose: a measurement in the DOPE inverted hexagonal phase.

Trehalose is a sugar which plays an important protectant role in organisms against damage due to dehydration. To explore the basic molecular mechanism which governs the protective function exerted on lipid membranes, X-ray diffraction and osmotic stress experiments have been performed on L: -alpha-dioleoyl-phosphatidyl-ethanolamine (DOPE) in trehalose solutions of different concentrations. In pure water, DOPE forms an inverted hexagonal (H(II)) phase; in sugar solutions, a strong dehydration, which induces a large reduction of the H(II) lattice parameter, has been detected, but nevertheless no phase transitions occur. Structural data, directly obtained from reconstructed electron density maps, show that the bending of the lipid monolayer induced by the sugar is coupled to changes in the DOPE molecular shape. By osmotic stress, the work required to dehydrate the monolayer has been obtained and the overall free energy described as a function of trehalose concentration. Three results should be stressed: (1) dehydration experiments performed in the presence of sugar demonstrate that the protective effect cannot be purely osmotic; (2) the pivotal surface, that location on the molecule whose area is invariant upon isothermal bending, has been analyzed by two different methods: the approach by Rand and co-workers and the approach by Templer and co-workers; in both cases its presence along the DOPE molecule has been revealed and its position estimated; (3) the spontaneous radius of curvature and the rigidity constant of the lipid monolayer, measured at the pivotal plane, changes from 3.06 nm (in pure water) to 2.82 nm (in 1.4 M trehalose), and from 0.55 x 10(-19) to 0.74 x 10(-19) J, respectively. We assume that these modifications are related to direct interactions between trehalose and DOPE that alter the interface geometry, reducing the repulsion between the polar heads. However, the increased bending rigidity also accounts for the changes of the property of the aqueous compartment, reflecting the rigidity and stiffness of the sugar matrix around and inside the lipid phase.

Lipid Bilayers↗

Lipid-based supramolecular systems for topical application: a preformulatory study.

This article describes the production and characterization of monoglyceride-based supramolecular systems by a simple processing technique, avoiding time-consuming procedures, high energy input, and the use of organic solvents. A preformulatory study was performed to study the influence of the experimental parameters on the production of monoglyceride-based disperse systems. In particular the effects of (1) stirring speed, (2) type and concentration of monoglyceride mixture, and (3) type and concentration of surfactant were investigated on the recovery, fraction of larger particles, mean diameter, and shape of smaller particles (so called nanosomes). Dispersions were first characterized by optical microscopy and freeze-fracture electron microscopy. The mean diameter of standard nanosomes, analyzed by photon correlation spectroscopy (PCS) after elimination of larger particles by filtration, was 193.5 nm. Cryotransmission electron microscopy studies, conducted in order to investigate the structure of dispersions, showed the coexistence of vesicles and particles characterized by a cubic organization. X-ray diffraction data revealed the coexistence of 2 different cubic phases, the first being a bicontinuous cubic phase of spatial symmetry Im3m (Q229) and the second belonging to the Pn3m spatial symmetry. A study on the stability of monoglyceride-based dispersions based on macroscopical analysis of organoleptic properties and dimensional analysis by time was performed after elimination of larger particles by filtration. Organoleptic and morphological features do not change by time, appearing free from phase-separation phenomena for almost 1 year from production. PCS studies showed that nanosomes undergo an initial increase in mean diameter within the first month following production; afterwards they generally maintain their dimensions for the next 4 months.

Chemistry, Pharmaceutical↗

Compressing inverse lyotropic systems: Structural behavior and energetics of dioleoyl phosphatidyl ethanolamine.

The pressure effects on the stability and energetics of lipid phases in the L-alpha-dioleoyl phosphatidyl ethanolamine (DOPE)-water system are presented. Using synchrotron diffraction experiments, performed at a wide range of concentrations, pressure-induced transitions from the inverse hexagonal (H(II)) to the lamellar L(alpha) phase and from the L(alpha) to the lamellar L(beta) phase are demonstrated. Moreover, in the most dehydrated samples an intermediate phase is found between the H(II) and the L(alpha) phases, confirming that the lamellar-to-nonlamellar phase transition occurs through key intermediate structures. Simple molecular packing arguments lead to an interpretation of the phase behavior: in fact, pressure induces a progressive stiffening of the DOPE hydrocarbon chains and a reduction of the cross-sectional area. Because pressure is more effective in reducing the cross-sectional area near the terminal methyl groups than at the water-lipid interface, the curvature of that interface in the H(II) phase is reduced during compression. The work of isothermal compression was then obtained and analyzed in terms of the elastic energetic contributions that should stabilize the DOPE phases during compression. As a result, we observe that the isothermal lateral compression modulus is almost independent of concentration, but it increases as a function of pressure, suggesting that the DOPE repulsion becomes very strong while the whole lipid shape becomes more cylindrical. On the other hand, the bending rigidity is observed to decrease with increasing pressure, while the spontaneous curvature becomes less negative. This suggests that the chain repulsion becomes relatively weaker, and thus less efficient in balancing the torque of head-group repulsion, as the order parameter increases.

Journal Article↗