Polimeri tiofenici funzionali e loro applicazioni nel fotovoltaico

Recentemente, sempre più attenzione è stata rivolta all' utilizzo di coloranti organici come assorbitori di luce per la preparazione di strati fotoattivi in celle solari organiche (OPV). I coloranti organici presentano un'elevata abilità nella cattura della luce solare grazie all'elevato coefficiente di estinzione molare e buone proprietà fotofisiche. Per questi motivi sono eccellenti candidati per l'incremento della conversione fotoelettrica in OPV. In questa tesi viene descritta una nuova strategia per l'incorporazione di derivati porfirinici in catena laterale a copolimeri tiofenici. Gli studi svolti hanno dimostrato che poli(3-bromoesil)tiofene può essere variamente funzionalizzato con idrossitetrafenilporfirina (TPPOH), per l'ottenimento di copolimeri utilizzabili come materiali p-donatori nella realizzazione di OPV. I copolimeri poli[3-(6-bromoesil)tiofene-co-(3-[5-(4-fenossi)-10,15,20-trifenilporfirinil]esil tiofene] P[T6Br-co-T6TPP] contenenti differenti quantità di porfirina, sono stati sintetizzati sia con metodi non regiospecifici che regiospecifici, con lo scopo di confrontarene le proprietà e di verificare se la strutture macromolecolare che presenta una regiochimica di sostituzione sempre uguale, promuove o meno il trasporto della carica elettrica, migliorando di conseguenza l'efficienza. E' stato inoltre effettuato un ulteriore confronto tra questi derivati e derivati simili P[T6H-co-T6TPP] che non contengono l'atomo di bromo in catena laterale con lo scopo di verificare se l'assenza del gruppo reattivo, migliora o meno la stabilità termica e chimica dei film polimerici, agendo favorevolmete sulle performance dei dispositivi fotovoltaici. Tutti i copolimeri sono stati caratterizzati con differenti tecniche: spettroscopia NMR, FT-IR e UV-Vis, analisi termiche DSC e TGA, e GPC. Le celle solari Bulk Heterojunction, preparate utilizzando PCBM come materiale elettron-accettore e i copolimeri come materilai elettron-donatori, sono state testate utilizzando un multimetro Keithley e il Solar Simulator.

Newly developed electrosynthesis of Layered Double Hydroxides: application to sensing, energy storage and conversion

Layered Double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, it does not usually allow for a fine control of the M(II)/M(III) ratio in the synthesized material and it is not suitable for large anions intercalation. Therefore, in this work a novel protocol has been proposed with the aim to overcome all these constraints using a method based on potentiodynamic synthesis. LDHs of controlled composition were prepared using different molar ratios of the trivalent to bivalent cations in the electrolytic solution ranging from 1:1 to 1:4. Moreover, we were able to produce electrochemically LDHs intercalated with carbon nanomaterials for the first time. A one-step procedure which contemporaneously allows for the Ni/Al-LDH synthesis, the reduction of graphene oxide (GO) and its intercalation inside the structure has been developed. The synthesised materials have been applied in several fields of interest. First of all, LDHs with a ratio 3:1 were exploited, and displayed good performances as catalysts for 5-(hydroxymethyl)furfural electro-oxidation, thus suggesting to carry out further investigation for applications in the field of industrial catalysis. The same materials, but with different metals ratios, were tested as catalysts for Oxygen Evolution Reaction, obtaining results comparable to LDHs synthesised by the classical co-precipitation method and also a better activity with respect to LDHs obtained by the potentiostatic approach. The composite material based on LDH and reduced graphene oxide was employed to fabricate a cathode of a hybrid supercapacitor coupled with an activated carbon anode. We can thus conclude that, to date, the potentiodynamic method has the greatest potential for the rapid synthesis of reproducible films of Co and Ni-based LDHs with controlled composition.

Conductive Polymer Composites

In recent years, nanotechnologies have led to the production of materials with new and sometimes unexpected qualities through the manipulation of nanoscale components. This research aimed primarily to the study of the correlation between hierarchical structures of hybrid organic-inorganic materials such as conductive polymer composites (CPCs). Using a bottom-up methodology, we could synthesize a wide range of inorganic nanometric materials with a high degree of homogeneity and purity, such as thiol capped metal nanoparticles, stoichiometric geomimetic chrysotile nanotubes and metal dioxide nanoparticles. It was also possible to produce inorganic systems formed from the interaction between the synthesized materials. These synthesized materials and others like multiwalled carbon nanotubes and grapheme oxide were used to produce conductive polymer composites. Electrospinning causes polymer fibers to become elongated using an electric field. This technique was used to produce fibers with a nanometric diameter of a polymer blend based on two different intrinsically conducting polymers polymers (ICPs): polyaniline (PANI) and poly(3-hexylthiophene) (P3HT). Using different materials as second phase in the initial electrospun polymer fibers caused significant changes to the material hierarchical structure, leading to the creation of CPCs with modified electrical properties. Further study of the properties of these new materials resulted in a better understanding of the electrical conductivity mechanisms in these electrospun materials.

Antipodal random sequences with prescribed second-order statistics: application to Compressive Sensing and UWB system based on DS-CDMA

It is usual to hear a strange short sentence: «Random is better than...». Why is randomness a good solution to a certain engineering problem? There are many possible answers, and all of them are related to the considered topic. In this thesis I will discuss about two crucial topics that take advantage by randomizing some waveforms involved in signals manipulations. In particular, advantages are guaranteed by shaping the second order statistic of antipodal sequences involved in an intermediate signal processing stages. The first topic is in the area of analog-to-digital conversion, and it is named Compressive Sensing (CS). CS is a novel paradigm in signal processing that tries to merge signal acquisition and compression at the same time. Consequently it allows to direct acquire a signal in a compressed form. In this thesis, after an ample description of the CS methodology and its related architectures, I will present a new approach that tries to achieve high compression by design the second order statistics of a set of additional waveforms involved in the signal acquisition/compression stage. The second topic addressed in this thesis is in the area of communication system, in particular I focused the attention on ultra-wideband (UWB) systems. An option to produce and decode UWB signals is direct-sequence spreading with multiple access based on code division (DS-CDMA). Focusing on this methodology, I will address the coexistence of a DS-CDMA system with a narrowband interferer. To do so, I minimize the joint effect of both multiple access (MAI) and narrowband (NBI) interference on a simple matched filter receiver. I will show that, when spreading sequence statistical properties are suitably designed, performance improvements are possible with respect to a system exploiting chaos-based sequences minimizing MAI only.

Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

Transport Properties and Novel Sensing Applications of Organic Semiconducting Crystals

The present thesis is focused on the study of Organic Semiconducting Single Crystals (OSSCs) and crystalline thin films. In particular solution-grown OSSC, e.g. 4-hdroxycyanobenzene (4HCB) have been characterized in view of their applications as novel sensors of X-rays, gamma-rays, alpha particles radiations and chemical sensors. In the field of ionizing radiation detection, organic semiconductors have been proposed so far mainly as indirect detectors, i.e. as scintillators or as photodiodes. I first study the performance of 4HCB single crystals as direct X-ray detector i.e. the direct photon conversion into an electrical signal, assessing that they can operate at room temperature and in atmosphere, showing a stable and linear response with increasing dose rate. A dedicated study of the collecting electrodes geometry, crystal thickness and interaction volume allowed us to maximize the charge collection efficiency and sensitivity, thus assessing how OSSCs perform at low operating voltages and offer a great potential in the development of novel ionizing radiation sensors. To better understand the processes generating the observed X-ray signal, a comparative study is presented on OSSCs based on several small-molecules: 1,5-dinitronaphthalene (DNN), 1,8-naphthaleneimide (NTI), Rubrene and TIPS-pentacene. In addition, the proof of principle of gamma-rays and alpha particles has been assessed for 4HCB single crystals. I have also carried out an investigation of the electrical response of OSSCs exposed to vapour of volatile molecules, polar and non-polar. The last chapter deals with rubrene, the highest performing molecular crystals for electronic applications. We present an investigation on high quality, millimeter-sized, crystalline thin films (10 – 100 nm thick) realized by exploiting organic molecular beam epitaxy on water-soluble substrates. Space-Charge-Limited Current (SCLC) and photocurrent spectroscopy measurements have been carried out. A thin film transistor was fabricated onto a Cytop® dielectric layer. The FET mobility exceeding 2 cm2/Vs, definitely assess the quality of RUB films.

Advanced electrospun nanofibrous mats for hindering delamination, improving damping and for sensing of composite laminates

Carbon Fiber Reinforced Polymers (CFRPs) display high specific mechanical properties, allowing the creation of lightweight components and products by metals replacement. To reach outstanding mechanical performances, the use of stiff thermoset matrices, like epoxy, is preferred. Laminated composites are commonly used for their ease of manipulation during object manufacturing. However, the natural anisotropic structure of laminates makes them vulnerable toward delamination. Moreover, epoxy-based CFRPs are very stiff materials, thus showing low damping capacity, which results in unwanted vibrations and structure-borne noise that may contribute to delamination triggering. Hence, searching for systems able to limit these drawbacks is of primary importance for safety reasons, as well as for economic ones. In this experimental thesis, the production and integration of innovative rubbery nanofibrous mats into CFRP laminates are presented. A smart approach, based on single-needle electrospinning of rubber-containing blends, is proposed for producing dimensionally stable rubbery nanofibers without the need for rubber crosslinking. Nano-modified laminates aim at obtaining structural composites with improved delamination resistance and enhanced damping capacity, without significantly lowering other relevant mechanical properties. The possibility of producing nanofibers nano-reinforced with graphene to be applied for reinforcing composite laminates is also investigated. Moreover, the use of piezoelectric nanofibrous mats in hybrid composite laminates for achieving self-sensing capability is presented too as a different approach to prevent the catastrophic consequences of possible structural laminate failure. Finally, an accurate, systematic, and critical study concerning tensile testing of nonwovens, using electrospun Nylon 66 random nanofibrous mats as a case study, is proposed. Nanofibers diameter and specimen geometry were investigated to thoroughly describe the nanomat tensile behaviour, also considering the polymer thermal properties, and the number of nanofibers crossings as a function of the nanofibers diameter. Stress-strain data were also analysed using a phenomenological data fitting model to interpret the tensile behaviour better.

“Nanoglial interfaces: nanostructured materials, interfaces and devices to unveil the role of astrocytes in brain function and dysfunction”

The role of non-neuronal brain cells, called astrocytes, is emerging as crucial in brain function and dysfunction, encompassing the neurocentric concept that was envisioning glia as passive components. Ion and water channels and calcium signalling, expressed in functional micro and nano domains, underpin astrocytes’ homeostatic function, synaptic transmission, neurovascular coupling acting either locally and globally. In this respect, a major issue arises on the mechanism through which astrocytes can control processes across scales. Finally, astrocytes can sense and react to extracellular stimuli such as chemical, physical, mechanical, electrical, photonic ones at the nanoscale. Given their emerging importance and their sensing properties, my PhD research program had the general goal to validate nanomaterials, interfaces and devices approaches that were developed ad-hoc to study astrocytes. The results achieved are reported in the form of collection of papers. Specifically, we demonstrated that i) electrospun nanofibers made of polycaprolactone and polyaniline conductive composites can shape primary astrocytes’ morphology, without affecting their function ii) gold coated silicon nanowires devices enable extracellular recording of unprecedented slow wave in primary differentiated astrocytes iii) colloidal hydrotalcites films allow to get insight in cell volume regulation process in differentiated astrocytes and to describe novel cytoskeletal actin dynamics iv) gold nanoclusters represent nanoprobe to trigger astrocytes structure and function v) nanopillars of photoexcitable organic polymer are potential tool to achieve nanoscale photostimulation of astrocytes. The results were achieved by a multidisciplinary team working with national and international collaborators that are listed and acknowledged in the text. Collectively, the results showed that astrocytes represent a novel opportunity and target for Nanoscience, and that Nanoglial interface might help to unveil clues on brain function or represent novel therapeutic approach to treat brain dysfunctions.

RICORDACI: Research on the Conservation, Restoration and Diagnosis of Cinematographic Films

This thesis is the result of the RICORDACI project, a three-year European-funded initiative involving the collaboration between the University of Bologna and the restoration laboratory of the Cineteca di Bologna, L'immagine Ritrovata, which aimed to develop innovative solutions and technologies for the preservation of cinematographic film heritage. In particular, this thesis presents new analytical methodologies to exploit two types of portable miniaturized Near Infrared spectrometers working in Diffuse Reflectance over the Short Wave Infrared (SWIR) range, to study the near infrared (NIR) spectral behavior of film base materials for an accurate, non-invasive and fast characterization of the polymer type; and for films with cellulose acetate supports, they can be employed as a diagnostic tool for monitoring the Degree of substitution (DS) affected by the loss of acetyl groups. The proposed methods offer non-invasive, fast, inexpensive and simple alternatives for the characterization and diagnosis of film bases to help the strategic planning and decision-making regarding storage, digitalization and intervention of film collections. Secondly, the thesis includes the evaluation of new green cleaning systems and solvents for the effective, fast and innocuous removal of undesired substances from degraded cinematographic films bases; these tests compared the efficiency of traditional systems and solvents against the new proposals. Firstly, the use of Deep Eutectic Solvent formulations for removing softened gelatin residues from cellulose nitrate bases; and secondly, the employment of green volatile solvents with different application methods, including the use of new electrospun nylon mats, for avoiding the dangerous use of friction for the removal of Triphenyl Phosphate blooms from the surface of cellulose acetate bases. The results obtained will help improving the efficiency of the interventions needed before the digitalization of historical cinematographic films and will pave the way for further investigation on the use of green solvents for cleaning polymeric heritage objects.

Design of luminescent metal complexes for polymer science

The program of my PhD studies has been dealing with the investigation of the research outcomes that may result from the use of luminescent Iridium(III) cyclometalated complexes in the field of polymer science. In particular, my activity has been focused on exploring two main applicative contexts, i.e. Ir(III) complexes for preparing polymers and in combination with polymers. In the first part, a new set of luminescent Ir(III) complexes was exploited as photocatalysts for light-assisted atom transfer radical polymerization of methyl methacrylate. The decoration of both cyclometalated and ancillary ligands with sp3 hybridized nitrogen substituents together with the use of specific counterions, imparted suitable photophysical and redox properties for an efficient photocatalyzed process. The second part has been focused on the employment of Ir(III) tetrazole complexes as phosphorescent dyes in polymeric materials. Colourless luminescent solar concentrators were prepared blending two Ir(III) cyclometalates with acrylate polymers. Their performances were investigated, leading to promising outcomes comparable, or superior, to those obtained from colourless LSCs based on organic fluorophores. As a complementary approach, Ir(III) complexes were covalently linked to polymers in the side chain, to obtain a new class of metallopolymers. To this extent, a bifunctional tetrazolate molecule, equipped with a coordination site and a polymerizable unit, was designed. The photophysical properties of the resultant luminescent polymeric films were discussed. In the end, an additional project involving both polymers and metal compounds was carried out during my experience as a visiting PhD student at Humboldt – University of Berlin. Polystyrene and polyethylene glycol -based ion-exchange resins were functionalized with peptides through a ligation pathway, for the selective chelation of Copper(II) in aqueous solutions. The coordinating capability of the materials towards Cu2+ ions was tested by ICP-MS analysis. The resins strategically modified with ion-selective peptides, may be exploited in the preparation of water-processing devices.