Luisa D’Urso

Probing the Sources of the Apparent Irreproducibility of Amyloid Formation: Drastic Changes in Kinetics and a Switch in Mechanism Due to Micellelike Oligomer Formation at Critical Concentrations of IAPP

The aggregation of amyloidogenic proteins is infamous for being highly chaotic, with small variations in conditions sometimes leading to large changes in aggregation rates. Using the amyloidogenic protein IAPP (islet amyloid polypeptide protein, also known as amylin) as an example, we show that a part of this phenomenon may be related to the formation of micellelike oligomers at specific critical concentrations and temperatures. We show that pyrene fluorescence can sensitively detect micellelike oligomer formation by IAPP and discriminate between micellelike oligomers from fibers and monomers, making pyrene one of the few chemical probes specific to a prefibrillar oligomer. We further show that oligomers of this type reversibly form at critical concentrations in the low micromolar range and at specific critical temperatures. Micellelike oligomer formation has several consequences for amyloid formation by IAPP. First, the kinetics of fiber formation increase substantially as the critical concentration is approached but are nearly independent of concentration below it, suggesting a direct role for the oligomers in fiber formation. Second, the critical concentration is strongly correlated with the propensity to form amyloid: higher critical concentrations are observed for both IAPP variants with lower amyloidogenicity and for native IAPP at acidic pH in which aggregation is greatly slowed. Furthermore, using the DEST NMR technique, we show that the pathway of amyloid formation switches as the critical point is approached, with self-interactions primarily near the N-terminus below the critical temperature and near the central region above the critical temperature, reconciling two apparently conflicting views of the initiation of IAPP aggregation.

Laser assisted green synthesis of free standing reduced graphene oxides at the water?air interface

A single step, scalable and green strategy has been developed to obtain reduced graphene oxide layers in water dispersion through nanosecond laser pulse irradiation of carbon targets. The layers spontaneously migrate at the water-air interface, forming sheets of several tens of micrometers and show intense ultraviolet photoluminescence. This unique condition offers an intriguing environment where opposing dielectric media meet and can be used in all those processes where molecular interactions such as hydrogen bonding and electrostatic interactions are greatly enhanced.

Controlled synthesis of carbon nanotubes and linear C chains by arc discharge in liquid nitrogen

Arc discharge between two graphite rods in liquid nitrogen has been investigated in order to identify the main factors ruling the formation of carbon nanotubes (CNTs) and linear C chains. The influence of the experimental parameters on the structural properties of the produced materials was evaluated and interpreted, taking into account the existing models. We found that the electrode size and discharge current values greatly influence the structural quality of the nanotubes (e.g., presence of carbonaceous impurities, innermost tube diameter) and a proper combination of these parameters allows one to control the synthesis of CNTs and/or CNT-linear C chain hybrid systems.

Laser processing of TiO2 colloids for an enhanced photocatalytic water splitting activity.

We have measured the photocatalytic water splitting activity of several titania colloids, modified by nanosecond pulsed laser irradiation. Photocatalysis has been tested using UV and visible light. We have found that laser irradiation increases the hydrogen production efficiency up to a factor of three for anatase, rutile and P25. A hydrogen production rate as high as 30mmolg-1h-1 has been obtained with good stability, tested by repeated runs. The chemical and morphological properties of the nanoparticles have been studied by electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy, showing that laser irradiation promotes the formation of disordered surface state and lattice distortion which could be responsible for the observed enhanced photocatalytic activity.