Synthetic and mechanistic investigation of new radical processes: reaction of organic azides with group-XIII Lewis acids

Dichloroindium hydride revealed to be a valid alternative to tributyltin hydride for radical reduction of organic (alkyl, aryl, acyl, solfonyl) azides. The new approach entails mild reaction conditions and provides high yields of the corresponding amines and amides, also showing high degrees of selectivity. The system dichloroindium hydride / azides can be utilised in fivemembered ring closures of g-azidonitriles, as a new source of aminyl radicals for the attractive synthesis of interesting amidine compounds in the absence of both toxic reagents and tedious purification procedures. Allylindium dichloride seems a good substitute for dichloroindium hydride for generation of indium centred radicals under photolytic conditions, since it allows allylation of electrophilic azides (e.g. phenylsulfonyl azide) and halogen or ester δ-substituted azides, the latter through a 1,5-H transfer rearrangement mechanism. Evidences of the radical nature of the reactions mechanism were provided by ESR spectroscopy, furthermore the same technique, allowed to discover that the reaction of azides with indium trichloride and other group XIII Lewis acids, in particular gallium trichloride, gives rise to strongly coloured, persistent paramagnetic species, whose structure is consistent with the radical cation of the head-to-tail dimer of the aniline corresponding to the starting azide.

Wireless Network Analytics for Next Generation Spectrum Awareness

The importance of networks, in their broad sense, is rapidly and massively growing in modern-day society thanks to unprecedented communication capabilities offered by technology. In this context, the radio spectrum will be a primary resource to be preserved and not wasted. Therefore, the need for intelligent and automatic systems for in-depth spectrum analysis and monitoring will pave the way for a new set of opportunities and potential challenges. This thesis proposes a novel framework for automatic spectrum patrolling and the extraction of wireless network analytics. It aims to enhance the physical layer security of next generation wireless networks through the extraction and the analysis of dedicated analytical features. The framework consists of a spectrum sensing phase, carried out by a patrol composed of numerous radio-frequency (RF) sensing devices, followed by the extraction of a set of wireless network analytics. The methodology developed is blind, allowing spectrum sensing and analytics extraction of a network whose key features (i.e., number of nodes, physical layer signals, medium access protocol (MAC) and routing protocols) are unknown. Because of the wireless medium, over-the-air signals captured by the sensors are mixed; therefore, blind source separation (BSS) and measurement association are used to estimate the number of sources and separate the traffic patterns. After the separation, we put together a set of methodologies for extracting useful features of the wireless network, i.e., its logical topology, the application-level traffic patterns generated by the nodes, and their position. The whole framework is validated on an ad-hoc wireless network accounting for MAC protocol, packet collisions, nodes mobility, the spatial density of sensors, and channel impairments, such as path-loss, shadowing, and noise. The numerical results obtained by extensive and exhaustive simulations show that the proposed framework is consistent and can achieve the required performance.