Design, synthesis and photovoltaic properties of some thiophene-based conjugated polymers for organic solar cells

The current issue of the resource of energy combined with the tendency to give a green footprint to our lifestyle have prompted the research to focus the attention on alternative sources with great strides in the optimization of polymeric photovoltaic devices. The research work described in this dissertation consists in the study of different semiconducting π-conjugated materials based on polythiophenes (Chapter I). In detail, the GRIM polymerization was deepened defining the synthetic conditions to obtain regioregular poly(3-alkylthiophene) (Chapter II). Since the use of symmetrical monomers functionalized with oxygen atom(s) allows to adopt easy synthesis leading to performing materials, disubstituted poly(3,4-dialkoxythiophene)s were successfully prepared, characterized and tested as photoactive materials in solar cells (Chapter III). A “green” resource of energy should be employed through sustainable devices and, for this purpose, the research work was continued on the synthesis of thiophene derivatives soluble in eco-friendly solvents. To make this possible, the photoactive layer was completely tailored starting from the electron-acceptor material. A fullerene derivative soluble in alcohols was successfully synthetized and adopted for the realization of the new devices (Chapter IV). New water/alcohol soluble electron-donor materials with different functional groups were prepared and their properties were compared (Chapter V). Once found the best ionic functional group, a new double-cable material was synthetized optimizing the surface area between the different materials (Chapter VI). Finally, other water/alcohol soluble materials were synthetized, characterized and used as cathode interlayers in eco-friendly devices (Chapter VII). In this work, all prepared materials were characterized by spectroscopy analyses, gel permeation chromatography and thermal analyses. Cyclic voltammetry, X-ray diffraction, atomic force microscopy and external quantum efficiency were used to investigate some peculiar aspects.

Toxic cyanobacteria in water intended for drinking purpose: improvement of cells and toxins’ analyses and of treatments for their removal

Massive proliferations of cyanobacteria in freshwaters have recently increased, causing ecological and economic losses. Their ever-increasing presence in water sources destined to potabilization has become a major threat for public health, since several species can produce harmful toxins (cyanotoxin). Therefore, additional specific measures to improve management and treatment of drinking water(s) are required. The PhD thesis investigates toxic cyanobacteria in drinking waters with a special focus on Emilia-Romagna (Italy), throughout three separated chapters, each with different specific objectives. The first chapter aims at improving the fast monitoring of cyanobacteria in drinking water, which was investigated by testing different models of multi-wavelength spectrofluorometers. Inter-laboratories calibrations were conducted using mono-specific cultures and field samples, and both the feasibility and the technical limitations of such tools were illustrated. The second chapter evaluates the effectiveness of drinking water treatments in removing cyanobacterial cells and toxins. Two chlorinated oxidants (sodium hypochlorite and chlorine dioxide) already in use for pre-oxidation during water potabilization, were tested on cultures of the toxic cyanobacterium Microcystis aeruginosa posing a specific focus on toxin removal and revealing that pre-oxidation can cause the release of toxins and unknown metabolites. Innovative treatments based on non-thermal plasma were also tested, observing an effective and rapid inactivation of cyanobacterial cells. The third chapter presents a study on a cyanobacterium isolated from a drinking water reservoir of Emilia-Romagna and investigated by combining biological, chemical, and genomic methods. Although the strain did not produce any known cyanotoxin, high toxicity of water-extract was observed in bioassays and potential implications for drinking water were discussed. Overall, the PhD thesis offers new insights into toxic cyanobacteria management in drinking water, highlighting best practices for drinking water managers regarding their detection and removal. Additionally, the thesis provides new contributions to the understanding of the freshwater cyanobacteria community in the Emilia-Romagna region.