Modifiche al protocollo di trasporto LTP per migliorarne le prestazioni in presenza di perdite elevate

La presente tesi si pone come obiettivo quello di analizzare il protocollo LTP (in particolare in ION) e proporre dei miglioramenti utili al caso in cui siano presenti perdite elevate. Piu in dettaglio, una prima parte introduttiva motiva l'inefficacia del TCP/IP in ambito interplanetario e introduce l'architettura DTN Bundle Protocol (Cap.1). La tesi prosegue con la descrizione delle specifiche del protocollo LTP (Cap.2), in particolar modo evidenziando come un bundle venga incapsulato in un blocco LTP, come questo sia successivamente diviso in tanti segmenti LTP e come questi vengano successivamente inviati con il protocollo UDP o con un protocollo analogo. Viene quindi presentata un'approfondita analisi delle penalizzazioni dovute alle perdite dei segmenti LTP, sia di tipo dati che di segnalazione (Cap. 3). Quest'analisi permette di dimostrare la criticita degli effetti delle perdite, in particolare per quello che riguarda i segmenti LTP di segnalazione. Mentre in presenza di perdite basse tali effetti hanno in media un impatto minimo sul tempo di consegna di un blocco LTP (quindi del bundle in esso contenuto), in quanto avvengono raramente, in presenza di perdite elevate rappresentano un collo di bottiglia per il tempo di consegna di un blocco LTP. A tal proposito sono state proposte alcune modifiche che permettono di migliorare le prestazioni di LTP (Cap. 4) compatibilmente con le specifiche RFC in modo da garantire l'interoperabilita con le diverse implementazioni del protocollo. Successivamente nel Cap. 5 viene mostrato come sono state implementate le modifiche proposte in ION 3.4.1. Nel capitolo finale (Cap. 6) sono presenti i risultati numerici relativi ad alcuni test preliminari eseguiti confrontando la versione originale del protocollo con le versioni modificate contenenti i miglioramenti proposti. I test sono risultati molto positivi per elevate perdite, confermando cosi la validita dell'analisi e dei miglioramenti introdotti.

Studio e ottimizzazione della produzione di radioisotopi per radiofarmaci mediante generatori compatti di neutroni

I generatori compatti di neutroni possono rappresentare un grande progresso nell'ambito della Medicina Nucleare. Sono una valida alternativa rispetto ai metodi tradizionali per la produzione dei radioisotopi necessari per la sintesi dei radiofarmaci, e permettono di esplorare e sviluppare nuove metodologie radioterapeutiche innovative, complementari e potenzialmente più efficaci rispetto a quelle già esistenti. Enea sta portando avanti due progetti in questo ambito. Il primo, SORGENTINA-RF, è volto allo sviluppo di una macchina in grado di produrre un fascio di neutroni a 14MeV, con la quale irradiare un target di molibdeno metallico, in modo da ottenere tecnezio-99 metastabile (99mTc), il radioisotopo più usato al mondo nelle procedure di imaging biomedico. Il secondo progetto, LINC-ER, ha lo scopo di progettare le infrastrutture necessarie ad accogliere un generatore compatto di neutroni, il cui scopo sarà quello di eliminare le residue cellule tumorali dopo un intervento chirurgico, a ferita aperta, in modo simile alle attuali tecniche di radioterapia intraoperatoria, che però sfruttano elettroni o raggi X. Questo lavoro di tesi trova posto in questi progetti perché ha contributo a portare avanti le ricerche in due aspetti specifici. Nel caso di SORGENTINA-RF, sono stati studiati tutti gli aspetti radiochimici per ottenere dal molibdeno metallico la soluzione liquida di molibdato sodico da cui si estrae il 99mTc. In questo caso si è deciso di puntare su processo “green” e innovativo basato sull’uso di perossido di idrogeno. Durante la tesi si sono studiati i più importanti fattori che governano questo processo e si è definito un meccanismo chimico che lo spiega. Nel caso di LINC-ER, invece, il lavoro sperimentale è stato quello di studiare metodi e rotte sintetiche nuove per ottenere nanoparticelle di composti di boro e bario, dispersi in hydrogels in grado di amplificare gli effetti del fascio neutronico sui tessuti cancerogeni e ridurli su quelli sani.

Inkjet-printed poly(N-isopropylacrylamide)/graphene electrodes for selective electroanalytical sensing

The main research topic of the present master thesis consisted in the modification and electrochemical testing of inkjet printed graphene electrodes with a thin polymeric hydrogel layer made of cross-linked poly(N-isopropylacrylamide) (PNIPAAM) acting as a functional layer to fabricate selective sensors. The first experimental activities dealt with the synthesis of the polymeric hydrogel and the modification of the active surface of graphene sensors through photopolymerization. Simultaneous inkjet printing and photopolymerization of the hydrogel precursor inks onto graphene demonstrated to be the most effective and reproducible technique for the modification of the electrode with PNIPAAM. The electrochemical performance of the modified electrodes was tested through cyclic voltammetry. Voltammograms with standard redox couples with either positive, neutral or negative charges, suggested an electrostatic filtering effect by the hydrogel blocking negatively charged redox species in near neutral pH electrolyte solutions from reaching the electrode surface. PNIPAAM is a known thermo-responsive polymer, but the variation of temperature did not influence the filtering properties of the hydrogels for the redox couples studied. However, a variation of the filter capacity of the material was observed at pH 2 in which the PNIPAAM hydrogel, most likely in protonated form, became impermeable to positively charged redox species and permeable to negatively charged species. Finally, the filtering capacity of the electrodes modified with PNIPAAM was evaluated for the electrochemical determination of analytes in presence of negatively charge potential interferents, such as antioxidants like ascorbic acid. The outcome of the final experiments suggested the possibility to use the inkjet-printed PNIPAAM thin layer for electroanalytical applications as an electrostatic filter against interferents of opposite charges, typically present in complex matrices, such as food and beverages.

Formulation of ionogel, hydrogel and films using a cellulose rich solid obtained from Pinus radiata

The purpose of my internship, carried out during my Erasmus period at the Complutense University of Madrid, was focused on the formulation of ionogels and hydrogels for the obtainment of films with high lignin content, and on their characterization measuring their antibacterial properties. For biomass formulation I used lignocellulosic biomass (Pinus Radiata) as raw material and ionic liquid as solvent. The two ionic liquids proposed were: 1-ethyl-3-methylimidazoliumdimethylphosphate [Emim][DMP] and 1-ethyl-3-methylimidazoliumdiethylphosphate [Emim][DEP]. The two-starting cellulose-rich solids were obtained from Pinus radiata wood that had been submitted to an organosolv process, to reduce its lignin content to fifteen (ORG15) and twenty per cent (ORG20). Having two ionic liquids and two solids available, the first phase of the project was devoted to the screening of both solids in both ionic liquids. Through this, it was possible to identify that only the [Emim][DMP] ionic liquid fulfils the purpose. It was also possible to discard the cellulose-rich solid ORG20 because its dissolution in the ionic liquid was not possible (after the time fixed) and, additionally, a Pinus radiata cellulose-rich solid bleached with hydrogen peroxide and containing ten per cent of lignin (ORG10B) was included in the screening. After screening, a total of five ionogels were subsequently formulated: two gels were formulated with the starting raw material ORG15 (with 1% and 1.75% cellulose, respectively) and three with ORG10B (with 1%, 1.75% and 3% cellulose, respectively). Five hydrogels were obtained from the ionogels. Rheological tests were performed on each ionogel and hydrogel. Finally, films were formulated from hydrogels and they were analysed by antibacterial testing to see if they could be applied as food packaging. In addition, antioxidant and properties such as opacity and transparency were also studied.

Development of an impedance based biosensor for studies of spheroids formation

Three-dimensional (3D) multicellular spheroids are exceptional in vitro cell models for their ability to accurately mimic real cell-cell interaction processes. However, the challenges in producing well-defined spheroids with controlled size together with the deficiency of techniques to monitor them significantly restrict their use. Herein, a novel device to study spheroid formation in real time is presented. By exploiting electrochemical impedance spectroscopy, a multi-electrode array (MEA) attached to a calcium alginate scaffold is able to monitor the behaviour of 36 different hydrogel wells. The scaffold contains inverted shape pyramidal microwells, which guide the aggregation of cells into spheroids with controlled dimensions. Preliminar studies on calcium alginate, optimisation of fabrication strategy are shown, together with testing of the device in the presence and the absence of the hydrogel. Lastly, the device was tested for its intended aim, i.e. to monitor the formation of a spheroid, proving its potential as an impedance biosensor.

Unibo-BP: an innovative free software implementation of Bundle Protocol Version 7 (RFC 9171)

The BP (Bundle Protocol) version 7 has been recently standardized by IETF in RFC 9171, but it is the whole DTN (Delay-/Disruption-Tolerant Networking) architecture, of which BP is the core, that is gaining a renewed interest, thanks to its planned adoption in future space missions. This is obviously positive, but at the same time it seems to make space agencies more interested in deployment than in research, with new BP implementations that may challenge the central role played until now by the historical BP reference implementations, such as ION and DTNME. To make Unibo research on DTN independent of space agency decisions, the development of an internal BP implementation was in order. This is the goal of this thesis, which deals with the design and implementation of Unibo-BP: a novel, research-driven BP implementation, to be released as Free Software. Unibo-BP is fully compliant with RFC 9171, as demonstrated by a series of interoperability tests with ION and DTNME, and presents a few innovations, such as the ability to manage remote DTN nodes by means of the BP itself. Unibo-BP is compatible with pre-existing Unibo implementations of CGR (Contact Graph Routing) and LTP (Licklider Transmission Protocol) thanks to interfaces designed during the thesis. The thesis project also includes an implementation of TCPCLv3 (TCP Convergence Layer version 3, RFC 7242), which can be used as an alternative to LTPCL to connect with proximate nodes, especially in terrestrial networks. Summarizing, Unibo-BP is at the heart of a larger project, Unibo-DTN, which aims to implement the main components of a complete DTN stack (BP, TCPCL, LTP, CGR). Moreover, Unibo-BP is compatible with all DTNsuite applications, thanks to an extension of the Unified API library on which DTNsuite applications are based. The hope is that Unibo-BP and all the ancillary programs developed during this thesis will contribute to the growth of DTN popularity in academia and among space agencies.