Synthesis of novel organic semiconductors for optoelectronic devices

This thesis describes the synthesis and characterisation of novel conjugated organic materials with optoelectronic application. The first chapter provides an introduction about organic semiconductors and in particular about their working principle from a physical and chemical point of view. An overview of the most common types of solar cells is provided, including examples of some of the best performing materials. The second chapter describes the synthesis of a new library of flavin derivatives as potential active materials for optoelectronic applications. Flavins are natural redox-active molecules, which show potential application in optoelectronics, thanks to their stability and versatility. FPF-Flavins, for instance, could be used either as acceptor units in push-pull polyconjugated systems or as acceptor unit in dyes for DSSCs. In the same chapter a first attempt of synthesising bis-flavins to be used as N-type semiconductors in BHJ devices is described. The third chapter describes the successful synthesis and characterization of a series of conjugated organic molecules based on the benzothiadiazole moiety. Among these, three molecules containing ferrocene as donor unit were tested as sensitizers for DSSCs, reporting a PCE of 0.3% as the best result. Further studies indicated a significant problem of charge recombination which limits the performance. A near-infrared absorbing push-pull polymer, based on BbT as acceptor unit, was also synthesised and tested in BHJ devices as P-type semiconductor in blend with PC71BM, showing a VOC of 0.71 V. Finally, the last chapter describes the synthesis of several tetrathiafulvalene derivatives in order to explore this moiety as donor unit in dyes for DSSCs and as HTM for perovskite-based solar cells. In particular, two very simple dyes were synthesised and implemented in DSSCs reporting a PCE 0.2% and 0.4%, respectively. The low efficiency was associated to the tendency to aggregate at the solid state, with the absorption shifting from the visible to the infrared range. A conjugated molecule, containing a DPP core, was also synthesised and tested as HTM for perovskite solar cells. The best reported PCE of 7.7% was obtained without any additives. A case study about dehalogenation and “halogen dance” in TTF iodide is also presented

An investigation of the roles furan versus thiophene π-bridges play in donor–π-acceptor porphyrin based DSSCs

Dye-sensitized solar cells (DSSCs) continue to attract interest due to their lower cost production compared to silicon based solar cells and their improving power conversion efficiencies. Porphyrin-based sensitizers have become an important sub-class due to their strong absorption characteristics in the visible region, convenient modulation of properties through synthetic manipulation and class-leading power conversion efficiencies. In this article, we report the synthesis and characterization of two porphyrin-based dyes and their application as sensitizers in DSSCs. A thiophene and a furan moiety have been incorporated into the push–pull architecture as a π-bridge, allowing the systematic investigation of how these moieties influence the physical properties of the dyes and the performance of their resulting DSSCs. A significant difference in PCEs has been observed, with the furan containing dye (PorF, PCE = 4.5%) being more efficient than the thiophene-based analogue (PorT, PCE = 3.6%) in conjunction with the iodide/triiodide redox electrolyte

Identification of peculiar gene expression profile in peripheral blood mononuclear cells (PBMC) of celiac patients on gluten free diet.

Celiac disease (CD) is a systemic disorder characterized by an immune-mediated reaction to gluten and a wide spectrum of clinical manifestations. Currently, the main treatment of CD is represented by adherence to a gluten-free diet (GFD) which determines the resolution of symptoms, and the normalization of the serology and of the duodenal villous atrophy. In the present study, we aimed to identify changes in gene expression in peripheral blood mononuclear cells (PBMCs) of celiac patients on GFD for at least 2 years, in order to identify novel disease biomarkers and candidate targets for putative therapeutic approaches. Microarray analysis was performed on PBMCs from 17 celiac patients on long-term GFD and 20 healthy controls. We identified 517 annotated genes that were significantly modulated between celiac patients and controls. Significant biological pathways were functionally clustered using the Core Function of Ingenuity System Pathway Analysis (IPA). Intriguingly, despite being on a GFD, celiac patients exhibited a peculiar PBMC profile characterized by an aberrant expression of genes involved in the regulation of immunity, inflammatory response, metabolism, and cell proliferation. Random forest algorithm was then used to validate the prediction ability of core genes as classifiers of the "celiac status". In conclusion, our study identified a characteristic PBMCs signature profile in clinically asymptomatic celiac patient

A BODIPY small molecule as hole transporting material for efficient perovskite solar cells

BODIPY-based materials are well known for their outstanding chemical and photo-stability as well as their ease of synthesis and tunability of their frontier molecular orbitals. These are attractive features for hole transporting materials (HTMs) for perovskite solar cells (PSCs) that could help improve device stability and cost. In this paper, we report the straightforward synthesis of a new BODIPY small molecule, PTZ-PTZ-BDP, functionalised with phenothiazine moieties in both the meso and α positions giving rise to a Y-shaped structure. As estimated by DFT calculations, and confirmed by electrochemical and ambient photoemission spectroscopy studies, PTZ-PTZ-BDP presents appropriate energy levels suitable for its use as a HTM in PSCs. Electrochemical measurements also reveal several redox processes with excellent reversibility. Systematic evaluation of its performance as HTM in n–i–p PSC with and without dopants was conducted and the device parameters compared with commonly used HTMs of spiro-OMeTAD and PTAA. The CH3NH3PbI3 based PSCs incorporating simple solution processed PTZ-PTZ-BDP as HTM demonstrated a champion power conversion efficiency of 14.6%, matched in performance and shelf-life stability to complex and expensive state-of-the-art HTMs, showing that BODIPY based HTMs are a promising direction for perovskite solar cells

Identification of miR-9-5p as direct regulator of ABCA1 and HDL-driven reverse cholesterol transport in circulating CD14+ cells of patients with metabolic syndrome.

AIMS: Metabolic syndrome (MS) is a cluster of cardio-metabolic risk factors associated with atherosclerosis and low-grade inflammation. Using unbiased expression screenings in peripheral blood mononuclear cells, we depict here a novel expression chart of 678 genes and 84 microRNAs (miRNAs) controlling inflammatory, immune and metabolic responses. In order to further elucidate the link between inflammation and the HDL cholesterol pathway in MS, we focussed on the regulation of the ATP-binding cassette transporter A1 (ABCA1), a key player in cholesterol efflux (CE). METHODS AND RESULTS: ABCA1 mRNA levels are suppressed in CD14+ cells of MS patients and are negatively correlated to body mass index (BMI), insulin-resistance (HOMA-IR) and cardiovascular risk, and positively to HDL cholesterol and CE. miRNA target in silico prediction identified a putative modulatory role of ABCA1 for the nuclear factor kappa-light-chain-enhancer of activated B cell (NF-κB) target miR-9-5p, whose expression pattern was up-regulated in CD14+ cells of MS patients, positively correlated to BMI, HOMA-IR, and triglycerides, and negatively to ABCA1 mRNA levels, HDL cholesterol and CE. Ectopic gain and loss of miR-9-5p function in macrophages modulated ABCA1 mRNA and protein levels, ABCA1 miRNA 3'-untranslated region target sequence reporter assay, and CE into HDL, thus confirming ABCA1 as a target of miR-9-5p. CONCLUSIONS: We identified the NF-κB target miR-9-5p as a negative regulator of ABCA1 adding a novel target pathway in the relationship between inflammation and HDL-driven reverse cholesterol transport for prevention or treatment of atherosclerosis in MS.N/

Identification of miR-9-5p as direct regulator of ABCA1 and HDL-driven reverse cholesterol transport in circulating CD14+ cells of patients with metabolic syndrome.

Aims: Metabolic syndrome (MS) is a cluster of cardio-metabolic risk factors associated with atherosclerosis and low-grade inflammation. Using unbiased expression screenings in peripheral blood mononuclear cells, we depict here a novel expression chart of 678 genes and 84 microRNAs (miRNAs) controlling inflammatory, immune and metabolic responses. In order to further elucidate the link between inflammation and the HDL cholesterol pathway in MS, we focussed on the regulation of the ATP-binding cassette transporter A1 (ABCA1), a key player in cholesterol efflux (CE). Methods and results: ABCA1 mRNA levels are suppressed in CD14+ cells of MS patients and are negatively correlated to body mass index (BMI), insulin-resistance (HOMA-IR) and cardiovascular risk, and positively to HDL cholesterol and CE. miRNA target in silico prediction identified a putative modulatory role of ABCA1 for the nuclear factor kappa-light-chain-enhancer of activated B cell (NF-κB) target miR-9-5p, whose expression pattern was up-regulated in CD14+ cells of MS patients, positively correlated to BMI, HOMA-IR, and triglycerides, and negatively to ABCA1 mRNA levels, HDL cholesterol and CE. Ectopic gain and loss of miR-9-5p function in macrophages modulated ABCA1 mRNA and protein levels, ABCA1 miRNA 3'-untranslated region target sequence reporter assay, and CE into HDL, thus confirming ABCA1 as a target of miR-9-5p. Conclusions: We identified the NF-κB target miR-9-5p as a negative regulator of ABCA1 adding a novel target pathway in the relationship between inflammation and HDL-driven reverse cholesterol transport for prevention or treatment of atherosclerosis in MS.N/

A poly(urethane)-encapsulated benzo[2,3-d:6,7-d']diimidazole organic down-converter for green hybrid LEDs

The development of organic down-converting materials continues to attract attention in hybrid LED technology by obviating the need for non-sustainable rare-earth elements. In this work, a benzodiimidazole-based system (TPA-BDI) has been employed as a down-converting layer in a hybrid organic-inorganic LED device. A commercially available poly(urethane)-based resin is used as the encapsulating material, providing a dilute layer of TPA-BDI that is deposited on top of the GaN-based LED. Crucially, the solution-state emissive performance is generally maintained when encapsulated at low concentrations within this resin. A maximum luminous efficacy of 87 lm W -1 was demonstrated using a 1.0 mg ml -1 concentration of TPA-BDI in the resin. The suitability of using organic down-converters to produce green light from hybrid devices was demonstrated by the excellent repeatability of the device characteristics across a series of encapsulated LEDs

Synergistic topological and supramolecular control of Diels-Alder reactivity based on a tunable self-complexing hos-guest molecular switch

International audienceCompartmentalization and binding‐triggered conformational change regulate many metabolic processes in living matter. Here, we have synergistically combined these two biorelevant processes to tune the Diels‐Alder (DA) reactivity of a synthetic self‐complexing host‐guest molecular switch CBPQT4+‐Fu, consisting of an electron‐rich furan unit covalently attached to the electron‐deficient cyclobis(paraquat‐p‐phenylene) tetrachloride (CBPQT4+, 4Cl‐) host. This design allows CBPQT4+‐Fu to efficiently compartmentalize the furan ring inside its host cavity in water, thereby protecting it from the DA reaction with maleimide. Remarkably, the self‐complexed CBPQT4+‐Fu can undergo a conformational change through intramolecular decomplexation upon the addition of a stronger binding molecular naphthalene derivative as a competitive guest, triggering the DA reaction upon addition of a chemical regulator. Remarkably, connecting the guest onto a thermoresponsive lower critical solution temperature (LCST) copolymer regulator controls the DA reaction on command upon heating and cooling the reaction media beyond and below the cloud point temperature of the copolymer, representing a rare example of decreased reactivity upon increasing temperature. Altogether, this work opens up new avenues towards combined topological and supramolecular control over reactivity in synthetic constructs enabling control over reactivity through molecular regulators or even mild temperature variations

Overcoming the mobility penalty introduced by dipole disorder in small-molecule HTM films

The importance of the hole-transport material (HTM) in perovskite solar cells (PSCs) is now very well-established, with state-of-the-art materials such as Spiro-OMeTAD attracting significant attention in the last decade. The high cost of such materials still limits the commercialisation of these HTMs. To tackle this, the amide linker has recently been introduced into HTM systems via EDOT-Amide-TPA, utilising condensation chemistry as a cheap and effective route to HTMs. EDOT-Amide-TPA is capable of a variety of intermolecular interactions such as dipole-dipole interactions and hydrogen bonding, both of which are beneficial for enhancing the film morphology and improving charge transport. However, the interplay between these different interactions is not trivial, and understanding how they affect each other is paramount to inform new HTM designs whilst minimising material waste. To date, studies investigating the combined effects of different intermolecular interactions within the HTL on the charge transport properties of these materials are lacking. Furthermore, dipole disorder within the film introduces a mobility ‘penalty’: mobility decreases with stronger overall dipole due to energetic disorder within the film, which hinders charge hopping. In this work, we investigate three amide-based HTM analogs with differing intermolecular interaction capabilities, and show that this penalty can be compensated by a preferentially increased dipole ordering, likely achieved through intermolecular hydrogen bonding. This effectively cancels out the dipole disorder while retaining the beneficial effects on the molecular packing. Our aim is that this work provides a good foundation for navigating the complex interplay between hydrogen bonding, dipole moments, conductivity, and film formation in small-molecule HTMs

Identification of peculiar gene expression profile in peripheral blood mononuclear cells (PBMC) of celiac patients on gluten free diet.

Celiac disease (CD) is a systemic disorder characterized by an immune-mediated reaction to gluten and a wide spectrum of clinical manifestations. Currently, the main treatment of CD is represented by adherence to a gluten-free diet (GFD) which determines the resolution of symptoms, and the normalization of the serology and of the duodenal villous atrophy. In the present study, we aimed to identify changes in gene expression in peripheral blood mononuclear cells (PBMCs) of celiac patients on GFD for at least 2 years, in order to identify novel disease biomarkers and candidate targets for putative therapeutic approaches. Microarray analysis was performed on PBMCs from 17 celiac patients on long-term GFD and 20 healthy controls. We identified 517 annotated genes that were significantly modulated between celiac patients and controls. Significant biological pathways were functionally clustered using the Core Function of Ingenuity System Pathway Analysis (IPA). Intriguingly, despite being on a GFD, celiac patients exhibited a peculiar PBMC profile characterized by an aberrant expression of genes involved in the regulation of immunity, inflammatory response, metabolism, and cell proliferation. Random forest algorithm was then used to validate the prediction ability of core genes as classifiers of the "celiac status". In conclusion, our study identified a characteristic PBMCs signature profile in clinically asymptomatic celiac patient