Ab-initio determination of x-ray absorption near edge structure (xanes) spectra in an ultrasoft and norm conserving pseudopotentials scheme

X-ray absorption spectroscopy (XAS) is a powerful means of investigation of structural and electronic properties in condensed -matter physics. Analysis of the near edge part of the XAS spectrum, the so – called X-ray Absorption Near Edge Structure (XANES), can typically provide the following information on the photoexcited atom: - Oxidation state and coordination environment. - Speciation of transition metal compounds. - Conduction band DOS projected on the excited atomic species (PDOS). Analysis of XANES spectra is greatly aided by simulations; in the most common scheme the multiple scattering framework is used with the muffin tin approximation for the scattering potential and the spectral simulation is based on a hypothetical, reference structure. This approach has the advantage of requiring relatively little computing power but in many cases the assumed structure is quite different from the actual system measured and the muffin tin approximation is not adequate for low symmetry structures or highly directional bonds. It is therefore very interesting and justified to develop alternative methods. In one approach, the spectral simulation is based on atomic coordinates obtained from a DFT (Density Functional Theory) optimized structure. In another approach, which is the object of this thesis, the XANES spectrum is calculated directly based on an ab – initio DFT calculation of the atomic and electronic structure. This method takes full advantage of the real many-electron final wavefunction that can be computed with DFT algorithms that include a core-hole in the absorbing atom to compute the final cross section. To calculate the many-electron final wavefunction the Projector Augmented Wave method (PAW) is used. In this scheme, the absorption cross section is written in function of several contributions as the many-electrons function of the finale state; it is calculated starting from pseudo-wavefunction and performing a reconstruction of the real-wavefunction by using a transform operator which contains some parameters, called partial waves and projector waves. The aim of my thesis is to apply and test the PAW methodology to the calculation of the XANES cross section. I have focused on iron and silicon structures and on some biological molecules target (myoglobin and cytochrome c). Finally other inorganic and biological systems could be taken into account for future applications of this methodology, which could become an important improvement with respect to the multiscattering approach.

Near field communication: Una tecnologia alla portata di tutti

Questa tesi ha lo scopo di analizzare e approfondire tutte le caratteristiche del nuovo standard delle comunicazioni a radiofrequenza: NFC. Per meglio comprendere l'argomento trattato ho suddiviso la tesi in 5 capitoli: Nel primo capitolo si effettuerà una panoramica sul mondo delle tecnologie a radiofrequenza: parleremo della tecnologia RFID, di come è nata e di come si è sviluppata dagli anni 60 ad oggi, di come veniva utilizzata un tempo e di come oggi viene usata. Ulteriore tecnologia a radiofrequenza presa in considerazione in questo capitolo è la tecnologia Bluetooth, di cui conosceremo le origini e l’evoluzione che ha subito nel corso degli anni. Nel secondo capitolo si affronterà l’argomento principale di questa tesi ossia la tecnologia NFC. Si analizzerà nel dettaglio, capiremo come è nata e come si è evoluta, vedremo come funziona nello specifico, che tipo di componenti usa e vedremo quali sono stati gli elementi cardine che hanno portato a questa rapida diffusione. Nel terzo capitolo si prenderà in esame un prototipo di applicazione per smartphone Android per meglio capire come effettivamente comunicano tra loro hardware e software. Il progetto prende il nome di WeMoNFC e permetterà di attivare e/o disattivare un particolare interruttore tramite l’accostamento di un tag NFC al telefono. Come richiama il nome, il progetto utilizzerà due componenti principali: il primo, ovviamente, è il modulo NFC inserito di fabbrica all’interno dello smartphone, il secondo invece è un dispositivo dell’azienda americana Belkin: il WeMo Switch. Nel quarto capitolo infine si trarranno le dovute conclusioni su questo argomento, si osserveranno i dati di mercato e si cercherà di ricavare una possibile ipotesi su come questa tecnologia davvero alla portata di tutti diverrà, più o meno, importante in un futuro prossimo.

Ingegnerizzazione e design di nanoparticelle core-shell di magnetite/silice

In the past decade the study of superparamagnetic nanoparticles has been intensively developed for many biomedical applications such as magnetically assisted drug delivery, MRI contrast agents, cells separation and hyperthermia therapy. All of these applications require nanoparticles with high magnetization, equipped also with a suitable surface coating which has to be non-toxic and biocompatible. In this master thesis, the silica coating of commercially available magnetic nanoparticles was investigated. Silica is a versatile material with many intrinsic features, such as hydrophilicity, low toxicity, proper design and derivatization yields particularly stable colloids even in physiological conditions. The coating process was applied to commercial magnetite particles dispersed in an aqueous solution. The formation of silica coated magnetite nanoparticles was performed following two main strategies: the Stöber process, in which the silica coating of the nanoparticle was directly formed by hydrolysis and condensation of suitable precursor in water-alcoholic mixtures; and the reverse microemulsions method in which inverse micelles were used to confine the hydrolysis and condensation reactions that bring to the nanoparticles formation. Between these two methods, the reverse microemulsions one resulted the most versatile and reliable because of the high control level upon monodispersity, silica shell thickness and overall particle size. Moving from low to high concentration, within the microemulsion region a gradual shift from larger particles to smaller one was detected. By increasing the amount of silica precursor the silica shell can also be tuned. Fluorescent dyes have also been incorporated within the silica shell by linking with the silica matrix. The structure of studied nanoparticles was investigated by using transmission electron microscope (TEM) and dynamic light scattering (DLS). These techniques have been used to monitor the syntetic procedures and for the final characterization of silica coated and silica dye doped nanoparticles. Finally, field dependent magnetization measurements showed the magnetic properties of core-shell nanoparticles were preserved. Due to a very well defined structure that combines magnetic and luminescent properties together with the possibility of further functionalization, these multifunctional nanoparticles are potentially useful platforms in biomedical fields such as labeling and imaging.