Selective localization of nanoparticles in microstructured systems

The research activities carried out during the doctoral program focused on selective localization of nanoparticles in microstructured polymer systems. Three distinct processes, very different from each other, were employed to achieve similar results. The first area of research has involved the selective localization of the carbon nanotubes within a biphasic and bicontinuous blend of polystyrene and polylactic acid, obtained by melt mixing the two thermoplastic polymers. Nanoparticles were selectively dispersed in the polystyrene phase achieving a lower percolation threshold than the initial one. In the second line of research, carried out in collaboration with the Soft Matter Physics group of the Adolphe Merkle Institute (Fribourg, Switzerland), hybrid organometallic perovkite nanocrystals were produced by precipitation in liquid phase. These nanocrystals were then incorporated into a thin film of polyethylene glycol diacrylate deposited by spin-coating on a glass substrate. The polymer crosslinking, triggered by exposure to an oxygen plasma, induced the formation of corrugations on the film surface (wrinkles) allowing the microstructuring of the perovskite. In the third line of research, carried out in collaboration with the National Institute of Optics (INO-CNR), selective localization of quantum dots in polydimethylsiloxane microlenses on a pyroelectric lithium niobate substrate were achieved through electrohydrodynamic and dielectrophoretic mechanisms. The lithium niobate substrate was periodically poled in an hexagonal pattern using finite element simulations to predict the final position of particles

On the Spraying Modality of Liquids by Pyroelectrohydrodynamics

We present for the first time an investigation on the spraying modality for the pyroelectrohydrodynamic (pyro-EHD) system. We show that the pyro-EHD spray (p-Spray) works well in the range from far field (d > 10 mm) to near field (d < 2 mm) without the need of external voltage and without the needs to change the experimental apparatus in that wide range of distances. Because the proposed method works without a counter electrode, no limitations are connected with the geometric shape of the substrate on which the spray coating is deposited. We report on several examples of the formation of disperse sprayed droplets, whose size can be varied between hundreds of micrometers and hundreds of nanometers, as well as on the production of sprayed pattern footpaths. The results reported here demonstrate the direct writing of spray patterns of nano/microdroplets with different materials in a very wide range, that is, from low- to high-viscous liquid solutions. Finally, as an example of application, we show the use of..

Discontinuation of first-line bevacizumab in metastatic colorectal cancer: the BEAWARE Italian Observational Study

BEAWARE investigated the pattern of first-line bevacizumab early interruption in the Italian real-world setting of metastatic colorectal cancer

Origin of Sn(II) oxidation in tin halide perovskites

Tin-halide perovskites have great potential as photovoltaic materials, but their performance is hampered by undesirable oxidation of Sn(ii) to Sn(iv). NMR proves DMSO to be a main cause of oxidation

Fluoride Chemistry in Tin Halide Perovskites

Tin is the frontrunner for substituting toxic lead in perovskite solar cells. However, tin suffers the detrimental oxidation of SnII to SnIV. Most of reported strategies employ SnF2 in the perovskite precursor solution to prevent SnIV formation. Nevertheless, the working mechanism of this additive remains debated. To further elucidate it, we investigate the fluoride chemistry in tin halide perovskites by complementary analytical tools. NMR analysis of the precursor solution discloses a strong preferential affinity of fluoride anions for SnIV over SnII, selectively complexing it as SnF4. Hard X-ray photoelectron spectroscopy on films shows the lower tendency of SnF4 than SnI4 to get included in the perovskite structure, hence preventing the inclusion of SnIV in the film. Finally, small-angle X-ray scattering reveals the strong influence of fluoride on the colloidal chemistry of precursor dispersions, directly affecting perovskite crystallization

Prognostic and predictive role of EGFR pathway alterations in biliary cancer patients treated with chemotherapy and anti-EGFR

The association of anti-EGFR to gemcitabine and oxaliplatin (GEMOX) chemotherapy did not improve survival in biliary tract carcinoma (BTC) patients. Multiple mechanisms might be involved in the resistance to anti-EGFR. Here, we explored the mutation profile of EGFR extracellular domain (ECD), of tyrosine kinase domain (TKD), and its amplification status. EGFR mutational status of exons 12, 18-21 was analyzed in 57 tumors by Sanger sequencing. EGFR amplification was evaluated in 37 tumors by Fluorescent In Situ Hybridization (FISH). Kaplan-Meier curves were calculated using the log-rank test. Six patients had mutations in exon 12 of EGFR ECD and 7 in EGFR TKD. Neither EGFR ECD nor TKD mutations affected progression free survival (PFS) or overall survival (OS) in the entire population. In the panitumumab plus GEMOX (P-GEMOX) arm, ECD mutated patients had a worse OS, while EGFR TKD mutated patients had a trend towards shorter PFS and OS. Overall, the presence of mutations in EGFR or in its transducers did not affect PFS or OS, while the extrahepatic cholangiocarcinoma (ECC) mutated patients had a worse prognosis compared to WT. Nineteen out of 37 tumors were EGFR amplified, but the amplification did not correlate with survival. ECC EGFR amplified patients had improved OS, whereas the amplification significantly correlated with poor PFS (p = 0.03) in gallbladder carcinoma patients. The high molecular heterogeneity is a predominant feature of BTC: the alterations found in this work seem to have a prognostic impact rather than a predictive role towards anti-EGFR therapy

Photovoltaic potential of tin perovskites revealed through layer-by-layer investigation of optoelectronic and charge transport properties

Tin perovskites are the most promising environmentally friendly alternative to lead perovskites. Among tin perovskites, FASnI3 (CH4N2SnI3) shows optimum band gap, and easy processability. However, the performance of FASnI3 based solar cells is incomparable to lead perovskites for several reasons, including energy band mismatch between the perovskite absorber film and the charge transporting layers (CTLs) for both types of carriers, i.e., for electrons (ETLs) and holes (HTLs). However, the band diagrams in the literature are inconsistent, and the charge extraction dynamics are poorly understood. In this paper, we study the energy band positions of FASnI3 based perovskites using Kelvin probe (KP) and photoelectron yield spectroscopy (PYS) to provide a precise band diagram of the most used device stack. In addition, we analyze the defects within the current energetic landscape of tin perovskites. We uncover the role of bathocuproine (BCP) in enhancing the electron extraction at the fullerene C60/BCP interface. Furthermore, we used transient surface photovoltage (tr-SPV) for the first time for tin perovskites to understand the charge extraction dynamics of the most reported HTLs such as NiOx and PEDOT, and ETLs such as C60, ICBA, and PCBM. Finally, we used Hall effect, KP, and time-resolved photoluminescence (TRPL) to estimate an accurate value of the p-doping concentration in FASnI3 and showed a consistent result of 1.5 * 1017 cm-3. Our findings prove that the energetic system of tin halide perovskites is deformed and should be redesigned independently from lead perovskites to unlock the full potential of tin perovskites.Comment: 22 pages, 5 figure

Fluoridchemie in Zinn‐Halogenid‐Perowskiten

Zinn ist der Top-Favorit für den Ersatz von giftigem Blei in Perowskit-Solarzellen. Allerdings kommt es dabei verstärkt zu der unerwünschten Oxidation von SnII zu SnIV. Die herkömmlichen Verfahren verwenden SnF2 in der Perowskit-Vorläuferlösung, um die Bildung von SnIV zu verhindern. Dennoch bleibt der Wirkmechanismus des Additivs unklar. Um diesen eingehender zu erläutern, untersuchen wir die Fluoridchemie in Zinn-Halogenid-Perowskiten mit einander ergänzenden Analyseverfahren. NMR-Spektroskopie der Vorläuferlösung offenbart eine stark bevorzugte Affinität der Fluoridanionen für SnIV gegenüber SnII, wodurch dieses selektiv als SnF4 komplexiert wird. Harte Röntgenphotoelektronenspektroskopie an Dünnschichten zeigt die geringere Bereitschaft von SnF4 gegenüber SnI4, in die Perowskit-Struktur eingebaut zu werden und verhindert somit den Einschluss von SnIV in der Dünnschicht. Abschließend offenbart Röntgen-Kleinwinkelstreuung den starken Einfluss vom Fluorid auf die kolloidale Chemie der Vorläuferlösungen, der sich direkt auf die darauffolgende Kristallisation auswirkt.European Research Council (ERC)Peer Reviewe

Cetuximab continuation after first progression in metastatic colorectal cancer (CAPRI-GOIM): A randomized phase II trial of FOLFOX plus cetuximab versus FOLFOX

Background: Cetuximab plus chemotherapy is a first-line treatment option in metastatic KRAS and NRAS wild-type colorectal cancer (CRC) patients. No data are currently available on continuing anti-epidermal growth factor receptor (EGFR) therapy beyond progression. Patients and methods: We did this open-label, 1:1 randomized phase II trial at 25 hospitals in Italy to evaluate the efficacy of cetuximab plus 5-fluorouracil, folinic acid and oxaliplatin (FOLFOX) as second-line treatment of KRAS exon 2 wild-type metastatic CRC patients treated in first line with 5-fluorouracil, folinic acid and irinotecan (FOLFIRI) plus cetuximab. Patients received FOLFOX plus cetuximab (arm A) or FOLFOX (arm B). Primary end point was progressionfree survival (PFS). Tumour tissues were assessed by next-generation sequencing (NGS). This report is the final analysis. Results: Between 1 February 2010 and 28 September 2014, 153 patients were randomized (74 in arm A and 79 in arm B). Median PFS was 6.4 [95% confidence interval (CI) 4.7-8.0] versus 4.5 months (95% CI 3.3-5.7); [hazard ratio (HR), 0.81; 95% CI 0.58-1.12; P = 0.19], respectively. NGS was performed in 117/153 (76.5%) cases; 66/117 patients (34 in arm A and 32 in arm B) had KRAS, NRAS, BRAF and PIK3CA wild-type tumours. For these patients, PFS was longer in the FOLFOX plus cetuximab arm [median 6.9 (95% CI 5.5-8.2) versus 5.3 months (95% CI 3.7-6.9); HR, 0.56 (95% CI 0.33-0.94); P = 0.025]. There was a trend in better overall survival: median 23.7 [(95% CI 19.4-28.0) versus 19.8 months (95% CI 14.9-24.7); HR, 0.57 (95% CI 0.32-1.02); P = 0.056]. Conclusions: Continuing cetuximab treatment in combination with chemotherapy is of potential therapeutic efficacy in molecularly selected patients and should be validated in randomized phase III trials