Processing of high resolution magic angle spinning spectra of breast cancer cells by the filter diagonalization method

Proton nuclear magnetic resonance (H-1 NMR) spectroscopy for detection of biochemical changes in biological samples is a successful technique. However, the achieved NMR resolution is not sufficiently high when the analysis is performed with intact cells. To improve spectral resolution, high resolution magic angle spinning (HR-MAS) is used and the broad signals are separated by a T-2 filter based on the CPMG pulse sequence. Additionally, HR-MAS experiments with a T-2 filter are preceded by a water suppression procedure. The goal of this work is to demonstrate that the experimental procedures of water suppression and T-2 or diffusing filters are unnecessary steps when the filter diagonalization method (FDM) is used to process the time domain HR-MAS signals. Manipulation of the FDM results, represented as a tabular list of peak positions, widths, amplitudes and phases, allows the removal of water signals without the disturbing overlapping or nearby signals. Additionally, the FDM can also be used for phase correction and noise suppression, and to discriminate between sharp and broad lines. Results demonstrate the applicability of the FDM post-acquisition processing to obtain high quality HR-MAS spectra of heterogeneous biological materials.

Use of Carr-Purcell pulse sequence with low refocusing flip angle to measure T-1 and T-2 in a single experiment

The Carr-Purcell pulse sequence, with low refocusing flip angle, produces echoes midway between refocusing pulses that decay to a minimum value dependent on T*(2). When the refocusing flip angle was pi/2 (CP90) and tau > T*(2), the signal after the minimum value, increased to reach a steady-state free precession regime (SSFP), composed of a free induction decay signal after each pulse and an echo, before the next pulse. When tau < T*(2), the signal increased from the minimum value to the steady-state regime with a time constant (T*) = 2T(1)T(2)/(T-1 + T-2). identical to the time constant observed in the SSFP sequence, known as the continuous wave free precession (CWFP). The steady-state amplitude obtained with M-cp90 = M0T2/(T-1+T-2) was identical to CWFP. Therefore, this sequence was named CP-CWFP because it is a Carr-Purcell sequence that produces results similar to the CWFP. However, CP-CWFP is a better sequence for measuring the longitudinal and transverse relaxation times in single scan, when the sample exhibits T-1 similar to T-2. Therefore, this sequence can be a useful method in time domain NMR and can be widely used in the agriculture, food and petrochemical industries because those samples tend to have similar relaxation times in low magnetic fields. (C) 2011 Elsevier Inc. All rights reserved.

Uso da RMN como um sensor online em processos industriais

Nuclear magnetic resonance (NMR) is one of the most versatile analytical techniques for chemical, biochemical and medical applications. Despite this great success, NMR is seldom used as a tool in industrial applications. The first application of NMR in flowing samples was published in 1951. However, only in the last ten years Flow NMR has gained momentum and new and potential applications have been proposed. In this review we present the historical evolution of flow or online NMR spectroscopy and imaging, and current developments for use in the automation of industrial processes.

Comparison of the reliability of multifocal visual evoked cortical potentials generated by pattern reversal and pattern pulse stimulation

This study compared the effectiveness of the multifocal visual evoked cortical potentials (mfVEP) elicited by pattern pulse stimulation with that of pattern reversal in producing reliable responses (signal-to-noise ratio >1.359). Participants were 14 healthy subjects. Visual stimulation was obtained using a 60-sector dartboard display consisting of 6 concentric rings presented in either pulse or reversal mode. Each sector, consisting of 16 checks at 99% Michelson contrast and 80 cd/m² mean luminance, was controlled by a binary m-sequence in the time domain. The signal-to-noise ratio was generally larger in the pattern reversal than in the pattern pulse mode. The number of reliable responses was similar in the central sectors for the two stimulation modes. At the periphery, pattern reversal showed a larger number of reliable responses. Pattern pulse stimuli performed similarly to pattern reversal stimuli to generate reliable waveforms in R1 and R2. The advantage of using both protocols to study mfVEP responses is their complementarity: in some patients, reliable waveforms in specific sectors may be obtained with only one of the two methods. The joint analysis of pattern reversal and pattern pulse stimuli increased the rate of reliability for central sectors by 7.14% in R1, 5.35% in R2, 4.76% in R3, 3.57% in R4, 2.97% in R5, and 1.78% in R6. From R1 to R4 the reliability to generate mfVEPs was above 70% when using both protocols. Thus, for a very high reliability and thorough examination of visual performance, it is recommended to use both stimulation protocols.

Detection of partial discharges at field in SF6 insulated equipments

This paper presents the results of research aiming to develop partial discharge detection techniques in high voltage equipment, at substation environment. Measurements of high frequency components of leakage current, at equipments' grounding conductor, were performed. This procedure was performed with the equipment energized and without disconnecting it from the system. The partial discharge generated current pulse is picked up by a high frequency CT, and is detected by an oscilloscope. The partial discharge identification was made considering previously obtained laboratory results, where partial discharges were characterized by means of its time domain signatures. This paper focuses measurements in SF6 circuit breakers. Encouraging results were obtained, showing the feasibility of detecting partial discharges in energized equipment in the laboratory and in the field, in a substation environment, using this method.

Applicazione ed integrazione di metodi di prospezione geofisica: studio idrogeofisico della Zona Insatura in condizioni idriche controllate

Il lavoro è incentrato sull’applicazione ed integrazione di differenti tecniche di indagine geofisica in campo ambientale e ingegneristico/archeologico. Alcuni esempi sono stati descritti al fine di dimostrare l’utilità delle metodologie geofisiche nella risoluzione di svariate problematiche. Nello specifico l’attenzione è stata rivolta all’utilizzo delle tecniche del Ground Penetrating Radar e del Time Domain Reflectometry in misure condotte su un corpo sabbioso simulante una Zona Insatura. L’esperimento è stato realizzato all’interno di un’area test costruita presso l’azienda agricola dell’Università La Tuscia di Viterbo. Hanno partecipato al progetto le Università di Roma Tre, Roma La Sapienza, La Tuscia, con il supporto tecnico della Sensore&Software. Nello studio è stato condotto un approccio definito idrogeofisico al fine di ottenere informazioni da misure dei parametri fisici relativi alla Zona Insatura simulata nell’area test. Il confronto e l’integrazione delle due differenti tecniche di indagine ha offerto la possibilità di estendere la profondità di indagine all’interno del corpo sabbioso e di verificare l’utilità della tecnica GPR nello studio degli effetti legati alle variazioni del contenuto d’acqua nel suolo, oltre a determinare la posizione della superficie piezometrica per i differenti scenari di saturazione. Uno specifico studio è stato realizzato sul segnale radar al fine di stabilire i fattori di influenza sulla sua propagazione all’interno del suolo. Il comportamento dei parametri dielettrici nelle condizioni di drenaggio e di imbibizione del corpo sabbioso è stato riprodotto attraverso una modellizzazione delle proprietà dielettriche ed idrologiche sulla base della dimensione, forma e distribuzione dei granuli di roccia e pori, nonché sulla base della storia relativa alla distribuzione dei fluidi di saturazione all’interno del mezzo. La modellizzazione è stata operata sulle basi concettuali del Differential Effective Medium Approximation.

Indagine delle proprietà statistiche di serie temporali di posizione applicata al caso della stazione permanente GPS della base Mario Zucchelli in Terra Vittoria (Antartide)

Da ormai sette anni la stazione permanente GPS di Baia Terranova acquisisce dati giornalieri che opportunamente elaborati consentono di contribuire alla comprensione della dinamica antartica e a verificare se modelli globali di natura geofisica siano aderenti all’area di interesse della stazione GPS permanente. Da ricerche bibliografiche condotte si è dedotto che una serie GPS presenta molteplici possibili perturbazioni principalmente dovute a errori nella modellizzazione di alcuni dati ancillari necessari al processamento. Non solo, da alcune analisi svolte, è emerso come tali serie temporali ricavate da rilievi geodetici, siano afflitte da differenti tipologie di rumore che possono alterare, se non opportunamente considerate, i parametri di interesse per le interpretazioni geofisiche del dato. Il lavoro di tesi consiste nel comprendere in che misura tali errori, possano incidere sui parametri dinamici che caratterizzano il moto della stazione permanente, facendo particolare riferimento alla velocità del punto sul quale la stazione è installata e sugli eventuali segnali periodici che possono essere individuati.

High-performance switching architectures for optical networks

The need for high bandwidth, due to the explosion of new multi\-media-oriented IP-based services, as well as increasing broadband access requirements is leading to the need of flexible and highly reconfigurable optical networks. While transmission bandwidth does not represent a limit due to the huge bandwidth provided by optical fibers and Dense Wavelength Division Multiplexing (DWDM) technology, the electronic switching nodes in the core of the network represent the bottleneck in terms of speed and capacity for the overall network. For this reason DWDM technology must be exploited not only for data transport but also for switching operations. In this Ph.D. thesis solutions for photonic packet switches, a flexible alternative with respect to circuit-switched optical networks are proposed. In particular solutions based on devices and components that are expected to mature in the near future are proposed, with the aim to limit the employment of complex components. The work presented here is the result of part of the research activities performed by the Networks Research Group at the Department of Electronics, Computer Science and Systems (DEIS) of the University of Bologna, Italy. In particular, the work on optical packet switching has been carried on within three relevant research projects: the e-Photon/ONe and e-Photon/ONe+ projects, funded by the European Union in the Sixth Framework Programme, and the national project OSATE funded by the Italian Ministry of Education, University and Scientific Research. The rest of the work is organized as follows. Chapter 1 gives a brief introduction to network context and contention resolution in photonic packet switches. Chapter 2 presents different strategies for contention resolution in wavelength domain. Chapter 3 illustrates a possible implementation of one of the schemes proposed in chapter 2. Then, chapter 4 presents multi-fiber switches, which employ jointly wavelength and space domains to solve contention. Chapter 5 shows buffered switches, to solve contention in time domain besides wavelength domain. Finally chapter 6 presents a cost model to compare different switch architectures in terms of cost.

Study of the thermal effects induced by magnetic resonance on endocardial leads: numerical models and experimental validation

Magnetic resonance imaging (MRI) is today precluded to patients bearing active implantable medical devices AIMDs). The great advantages related to this diagnostic modality, together with the increasing number of people benefiting from implantable devices, in particular pacemakers(PM)and carioverter/defibrillators (ICD), is prompting the scientific community the study the possibility to extend MRI also to implanted patients. The MRI induced specific absorption rate (SAR) and the consequent heating of biological tissues is one of the major concerns that makes patients bearing metallic structures contraindicated for MRI scans. To date, both in-vivo and in-vitro studies have demonstrated the potentially dangerous temperature increase caused by the radiofrequency (RF) field generated during MRI procedures in the tissues surrounding thin metallic implants. On the other side, the technical evolution of MRI scanners and of AIMDs together with published data on the lack of adverse events have reopened the interest in this field and suggest that, under given conditions, MRI can be safely performed also in implanted patients. With a better understanding of the hazards of performing MRI scans on implanted patients as well as the development of MRI safe devices, we may soon enter an era where the ability of this imaging modality may be more widely used to assist in the appropriate diagnosis of patients with devices. In this study both experimental measures and numerical analysis were performed. Aim of the study is to systematically investigate the effects of the MRI RF filed on implantable devices and to identify the elements that play a major role in the induced heating. Furthermore, we aimed at developing a realistic numerical model able to simulate the interactions between an RF coil for MRI and biological tissues implanted with a PM, and to predict the induced SAR as a function of the particular path of the PM lead. The methods developed and validated during the PhD program led to the design of an experimental framework for the accurate measure of PM lead heating induced by MRI systems. In addition, numerical models based on Finite-Differences Time-Domain (FDTD) simulations were validated to obtain a general tool for investigating the large number of parameters and factors involved in this complex phenomenon. The results obtained demonstrated that the MRI induced heating on metallic implants is a real risk that represents a contraindication in extending MRI scans also to patient bearing a PM, an ICD, or other thin metallic objects. On the other side, both experimental data and numerical results show that, under particular conditions, MRI procedures might be consider reasonably safe also for an implanted patient. The complexity and the large number of variables involved, make difficult to define a unique set of such conditions: when the benefits of a MRI investigation cannot be obtained using other imaging techniques, the possibility to perform the scan should not be immediately excluded, but some considerations are always needed.

Partial discharge in power distribution electrical systems: pulse propagation models and detection optimization

Investigation on impulsive signals, originated from Partial Discharge (PD) phenomena, represents an effective tool for preventing electric failures in High Voltage (HV) and Medium Voltage (MV) systems. The determination of both sensors and instruments bandwidths is the key to achieve meaningful measurements, that is to say, obtaining the maximum Signal-To-Noise Ratio (SNR). The optimum bandwidth depends on the characteristics of the system under test, which can be often represented as a transmission line characterized by signal attenuation and dispersion phenomena. It is therefore necessary to develop both models and techniques which can characterize accurately the PD propagation mechanisms in each system and work out the frequency characteristics of the PD pulses at detection point, in order to design proper sensors able to carry out PD measurement on-line with maximum SNR. Analytical models will be devised in order to predict PD propagation in MV apparatuses. Furthermore, simulation tools will be used where complex geometries make analytical models to be unfeasible. In particular, PD propagation in MV cables, transformers and switchgears will be investigated, taking into account both irradiated and conducted signals associated to PD events, in order to design proper sensors.

Calibrazione di modelli idrologici con algoritmi multiobiettivo

Traditional procedures for rainfall-runoff model calibration are generally based on the fit of the individual values of simulated and observed hydrographs. It is used here an alternative option that is carried out by matching, in the optimisation process, a set of statistics of the river flow. Such approach has the additional, significant advantage to allow also a straightforward regional calibration of the model parameters, based on the regionalisation of the selected statistics. The minimisation of the set of objective functions is carried out by using the AMALGAM algorithm, leading to the identification of behavioural parameter sets. The procedure is applied to a set of river basins located in central Italy: the basins are treated alternatively as gauged and ungauged and, as a term of comparison, the results obtained with a traditional time-domain calibration is also presented. The results show that a suitable choice of the statistics to be optimised leads to interesting results in real world case studies as far as the reproduction of the different flow regimes is concerned.

Collective effects for the LHC injectors: non-ultrarelativistic approaches

The upgrade of the CERN accelerator complex has been planned in order to further increase the LHC performances in exploring new physics frontiers. One of the main limitations to the upgrade is represented by the collective instabilities. These are intensity dependent phenomena triggered by electromagnetic fields excited by the interaction of the beam with its surrounding. These fields are represented via wake fields in time domain or impedances in frequency domain. Impedances are usually studied assuming ultrarelativistic bunches while we mainly explored low and medium energy regimes in the LHC injector chain. In a non-ultrarelativistic framework we carried out a complete study of the impedance structure of the PSB which accelerates proton bunches up to 1.4 GeV. We measured the imaginary part of the impedance which creates betatron tune shift. We introduced a parabolic bunch model which together with dedicated measurements allowed us to point to the resistive wall impedance as the source of one of the main PSB instability. These results are particularly useful for the design of efficient transverse instability dampers. We developed a macroparticle code to study the effect of the space charge on intensity dependent instabilities. Carrying out the analysis of the bunch modes we proved that the damping effects caused by the space charge, which has been modelled with semi-analytical method and using symplectic high order schemes, can increase the bunch intensity threshold. Numerical libraries have been also developed in order to study, via numerical simulations of the bunches, the impedance of the whole CERN accelerator complex. On a different note, the experiment CNGS at CERN, requires high-intensity beams. We calculated the interpolating Hamiltonian of the beam for highly non-linear lattices. These calculations provide the ground for theoretical and numerical studies aiming to improve the CNGS beam extraction from the PS to the SPS.

Rheology and Fourier-transform rheology on water-based systems

The influence of shear fields on water-based systems was investigated within this thesis. The non-linear rheological behaviour of spherical and rod-like particles was examined with Fourier-Transform rheology under LAOS conditions. As a model system for spherical particles two different kinds of polystyrene dispersions, with a solid content higher than 0.3 each, were synthesised within this work. Due to the differences in polydispersity and Debye-length, differences were also found in the rheology. In the FT-rheology both kinds of dispersions showed a similar rise in the intensities of the magnitudes of the odd higher harmonics, which were predicted by a model. The in some cases additionally appearing second harmonics were not predicted. A novel method to analyse the time domain signal was developed, that splits the time domain signal up in four characteristic functions. Those characteristic functions correspond to rheological phenomena. In some cases the intensities of the Fourier components can interfere negatively. FD-virus particles were used as a rod-like model system, which already shows a highly non-linear behaviour at concentrations below 1. % wt. Predictions for the dependence of the higher harmonics from the strain amplitude described the non-linear behaviour well at large, but no so good at small strain amplitudes. Additionally the trends of the rheological behaviour could be described by a theory for rod-like particles. An existing rheo-optical set-up was enhanced by reducing the background birefringence by a factor of 20 and by increasing the time resolution by a factor of 24. Additionally a combination of FT-rheology and rheo-optics was achieved. The influence of a constant shear field on the crystallisation process of zinc oxide in the presence of a polymer was examined. The crystallites showed a reduction in length by a factor of 2. The directed addition of polymers in combination with a defined shear field can be an easy way for a defined change of the form of crystallites.

Advanced signal and receiver design for next generation OFDM systems

This thesis deal with the design of advanced OFDM systems. Both waveform and receiver design have been treated. The main scope of the Thesis is to study, create, and propose, ideas and novel design solutions able to cope with the weaknesses and crucial aspects of modern OFDM systems. Starting from the the transmitter side, the problem represented by low resilience to non-linear distortion has been assessed. A novel technique that considerably reduces the Peak-to-Average Power Ratio (PAPR) yielding a quasi constant signal envelope in the time domain (PAPR close to 1 dB) has been proposed.The proposed technique, named Rotation Invariant Subcarrier Mapping (RISM),is a novel scheme for subcarriers data mapping,where the symbols belonging to the modulation alphabet are not anchored, but maintain some degrees of freedom. In other words, a bit tuple is not mapped on a single point, rather it is mapped onto a geometrical locus, which is totally or partially rotation invariant. The final positions of the transmitted complex symbols are chosen by an iterative optimization process in order to minimize the PAPR of the resulting OFDM symbol. Numerical results confirm that RISM makes OFDM usable even in severe non-linear channels. Another well known problem which has been tackled is the vulnerability to synchronization errors. Indeed in OFDM system an accurate recovery of carrier frequency and symbol timing is crucial for the proper demodulation of the received packets. In general, timing and frequency synchronization is performed in two separate phases called PRE-FFT and POST-FFT synchronization. Regarding the PRE-FFT phase, a novel joint symbol timing and carrier frequency synchronization algorithm has been presented. The proposed algorithm is characterized by a very low hardware complexity, and, at the same time, it guarantees very good performance in in both AWGN and multipath channels. Regarding the POST-FFT phase, a novel approach for both pilot structure and receiver design has been presented. In particular, a novel pilot pattern has been introduced in order to minimize the occurrence of overlaps between two pattern shifted replicas. This allows to replace conventional pilots with nulls in the frequency domain, introducing the so called Silent Pilots. As a result, the optimal receiver turns out to be very robust against severe Rayleigh fading multipath and characterized by low complexity. Performance of this approach has been analytically and numerically evaluated. Comparing the proposed approach with state of the art alternatives, in both AWGN and multipath fading channels, considerable performance improvements have been obtained. The crucial problem of channel estimation has been thoroughly investigated, with particular emphasis on the decimation of the Channel Impulse Response (CIR) through the selection of the Most Significant Samples (MSSs). In this contest our contribution is twofold, from the theoretical side, we derived lower bounds on the estimation mean-square error (MSE) performance for any MSS selection strategy,from the receiver design we proposed novel MSS selection strategies which have been shown to approach these MSE lower bounds, and outperformed the state-of-the-art alternatives. Finally, the possibility of using of Single Carrier Frequency Division Multiple Access (SC-FDMA) in the Broadband Satellite Return Channel has been assessed. Notably, SC-FDMA is able to improve the physical layer spectral efficiency with respect to single carrier systems, which have been used so far in the Return Channel Satellite (RCS) standards. However, it requires a strict synchronization and it is also sensitive to phase noise of local radio frequency oscillators. For this reason, an effective pilot tone arrangement within the SC-FDMA frame, and a novel Joint Multi-User (JMU) estimation method for the SC-FDMA, has been proposed. As shown by numerical results, the proposed scheme manages to satisfy strict synchronization requirements and to guarantee a proper demodulation of the received signal.

Electronic energy transfer processes and charge carrier transport in pi-conjugated polymers

Conjugated polymers have attracted tremendous academical and industrial research interest over the past decades due to the appealing advantages that organic / polymeric materials offer for electronic applications and devices such as organic light emitting diodes (OLED), organic field effect transistors (OFET), organic solar cells (OSC), photodiodes and plastic lasers. The optimization of organic materials for applications in optoelectronic devices requires detailed knowledge of their photophysical properties, for instance energy levels of excited singlet and triplet states, excited state decay mechanisms and charge carrier mobilities. In the present work a variety of different conjugated (co)polymers, mainly polyspirobifluorene- and polyfluorene-type materials, was investigated using time-resolved photoluminescence spectroscopy in the picosecond to second time domain to study their elementary photophysical properties and to get a deeper insight into structure-property relationships. The experiments cover fluorescence spectroscopy using Streak Camera techniques as well as time-delayed gated detection techniques for the investigation of delayed fluorescence and phosphorescence. All measurements were performed on the solid state, i.e. thin polymer films and on diluted solutions. Starting from the elementary photophysical properties of conjugated polymers the experiments were extended to studies of singlet and triplet energy transfer processes in polymer blends, polymer-triplet emitter blends and copolymers. The phenomenon of photonenergy upconversion was investigated in blue light-emitting polymer matrices doped with metallated porphyrin derivatives supposing an bimolecular annihilation upconversion mechanism which could be experimentally verified on a series of copolymers. This mechanism allows for more efficient photonenergy upconversion than previously reported for polyfluorene derivatives. In addition to the above described spectroscopical experiments, amplified spontaneous emission (ASE) in thin film polymer waveguides was studied employing a fully-arylated poly(indenofluorene) as the gain medium. It was found that the material exhibits a very low threshold value for amplification of blue light combined with an excellent oxidative stability, which makes it interesting as active material for organic solid state lasers. Apart from spectroscopical experiments, transient photocurrent measurements on conjugated polymers were performed as well to elucidate the charge carrier mobility in the solid state, which is an important material parameter for device applications. A modified time-of-flight (TOF) technique using a charge carrier generation layer allowed to study hole transport in a series of spirobifluorene copolymers to unravel the structure-mobility relationship by comparison with the homopolymer. Not only the charge carrier mobility could be determined for the series of polymers but also field- and temperature-dependent measurements analyzed in the framework of the Gaussian disorder model showed that results coincide very well with the predictions of the model. Thus, the validity of the disorder concept for charge carrier transport in amorphous glassy materials could be verified for the investigated series of copolymers.