Electron Donor-Acceptor Spirobi[cyclopenta[2,1-b:3,4-b’] dithiophene Derivatives as Precursors of Electrodeposited Regioregular Thiophene-based Polymers

A series of conjugation extended push-pull derivatives of 4,4′-spirobi[cyclopenta[2,1-b : 3,4-b′]dithiophene] were synthesized and fully characterized, in which each perpendicularly aligned cyclopenta[2,1-b : 3,4-b′]dithiophene features a pendant dicyanovinylene as an electron acceptor and a thiophene as an electron donor. The electrochemical and photophysical properties of the new molecules, which differ from each other for the presence and/or location of an additional n-hexyl chain on the pendant thiophene unit, were investigated, as well as their susceptibility to electrochemical polymerization. The substitution arrangement of the monomers was found to exert significant influence on the outcome of the electropolymerization process and on the optoelectronic properties and morphological film characteristics of the new regioregular materials obtained.Fil: Minudri, Daniela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Orlandi, Simonetta. Consiglio Nazionale delle Ricerche; ItaliaFil: Cavazzini, Marco. Consiglio Nazionale delle Ricerche; ItaliaFil: Rossi, Sergio. Università degli Studi di Milano; ItaliaFil: Marzari, Gabriela Lorena. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Cavallo, Pablo César. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Fernandez, Luciana Andrea. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Fungo, Fernando Gabriel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Pozzi, Gianluca. Consiglio Nazionale delle Ricerche; Itali

Improving the Electropolymerization Properties of Fluorene-Bridged Dicarbazole Monomers through Polyfluoroalkyl Side Chains

The facile functionalization of the fluorene scaffold at the 2,7-positions was utilized to provide access to two soluble carbazole-π-carbazole derivatives CFC-H1 and CFC-F1 featuring fully hydrogenated and polyfluorinated alkyl chains at the 9-position of the fluorene π-bridging unit, respectively. The optical and electrochemical properties of the new dicarbazoles were investigated. Their electrochemical polymerization over Pt and indium tin oxide electrodes allowed the generation of electroactive polymeric films, whose physicochemical characteristics were strongly dependent on the kind of alkyl chain present on the fluorene bridge. In particular, the electropolymerization of the polyfluorinated monomer allowed the fabrication of thin films with good electrical conductivity, reversible electrochemical processes, good electrochromic properties, and enhanced water repellency with respect to its nonfluorinated analogue.Fil: Pecnikaj, Ilir. Consiglio Nazionale delle Ricerche; ItaliaFil: Orlandi, Simonetta. Consiglio Nazionale delle Ricerche; ItaliaFil: Pozzi, Gianluca. Consiglio Nazionale delle Ricerche; ItaliaFil: Cappellari, María Victoria. Universidad Nacional de Rio Cuarto. Facultad de Cs.exactas Fisicoquimicas y Naturales. Instituto de Investigaciones En Tecnologias Energeticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Cordoba. Instituto de Investigaciones En Tecnologias Energeticas y Materiales Avanzados.; ArgentinaFil: Marzari, Gabriela Lorena. Universidad Nacional de Rio Cuarto. Facultad de Cs.exactas Fisicoquimicas y Naturales. Instituto de Investigaciones En Tecnologias Energeticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Cordoba. Instituto de Investigaciones En Tecnologias Energeticas y Materiales Avanzados.; ArgentinaFil: Fernandez, Luciana Andrea. Universidad Nacional de Rio Cuarto. Facultad de Cs.exactas Fisicoquimicas y Naturales. Instituto de Investigaciones En Tecnologias Energeticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Cordoba. Instituto de Investigaciones En Tecnologias Energeticas y Materiales Avanzados.; ArgentinaFil: Zensich, Maximiliano Andres. Universidad Nacional de Río Cuarto; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Hernandez, Laura. Universidad Nacional de Río Cuarto; ArgentinaFil: Fungo, Fernando Gabriel. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentin

Fashioning Fluorous Organic Spacers for Tunable and Stable Layered Hybrid Perovskites

Two dimensional (2D) organic-inorganic hybrid perovskites have recently attracted enormous attention due to their higher environmental stability with respect to three-dimensional (3D) perovskites and larger structural tunability. The layered structure relaxes constraints on the dimensions of the organic cations that alternate the inorganic sheets, opening up a large choice on the organics, ultimately enabling the creation of tunable layered perovskites. Here, we report on a series of fluorous cations, varying in size and shape, as building blocks for a new family of fluorous 2D lead-iodide perovskites. These display a large tunability in the optical and dielectric properties depending on the structure of the fluorous cations. Importantly, despite the invariant inorganic framework, the 2D perovskite electronic structure is strongly affected by the cation size. The longer the cation, the smaller the 2D perovskite band gap and the exciton binding energy (reducing from 400 meV down to 130 meV). Such variation is induced by the strain in the inorganic sheet, resulting in a more dispersed valence and conduction bands, in turn yielding a smaller band gap. In addition, a smaller effective mass for the 2D perovskite with the longest cation is calculated, for which improved transport properties are anticipated. Importantly, the fluorous moiety confers extreme stability to the 2D perovskite and enhances the hydrophobic character of the perovskite surface, which remains perfectly stable for more than one month in ambient conditions

Operative blood loss and use of blood products after full robotic and conventional low anterior resection with total mesorectal excision for treatment of rectal cancer

To date, no studies have investigated the estimated blood loss (EBL) after full robotic low anterior resection (R-LAR) in a case-matched model, comparing it with the conventional open approach (O-LAR). Forty-nine patients in the R-LAR and 105 in the O-LAR group were matched for age, gender, BMI (body mass index), ASA (American Society of Anesthesiology) class, tumor–node–metastasis (TNM) classification and UICC (Union for International Cancer Control) stage, distance of the lower edge of the tumor from the anal verge, presence of comorbidities, and preoperative hemoglobin (Hb). EBL was significantly higher in the O-LAR group (P < 0.001); twelve units of packed red blood cells were globally transfused in the O-LAR group, compared to one unit only in the R-LAR (P = 0.051). A significantly higher postoperative Hb drop (3.0 vs. 2.4 g/dL, P = 0.015) was registered in the O-LAR patients. The length of hospital stay was much lower for the R-LAR group (8.4 vs. 12.4 days, P < 0.001). The number of harvested lymph nodes (17.4 vs. 13.5, P = 0.006) and extent of distal margin (2.9 vs. 1.9 cm, P < 0.001) were significantly higher in the R-LAR group. Open surgery was confirmed as the sole variable significantly associated (P < 0.001) with blood loss (odds ratio = 4.41, 95% CI 2.06–9.43). It was a confirmed prognosticator of blood loss (P = 0.006) when a preoperative clinical predictive model was built, using multivariate analysis (odds ratio = 3.95, 95% CI 1.47–10.6). In conclusion, R-LAR produced less operative blood loss and less drop in postoperative hemoglobin when compared to O-LAR. Other clinically relevant outcomes were similar or superior to O-LAR

Shedding light on typical species : implications for habitat monitoring

Habitat monitoring in Europe is regulated by Article 17 of the Habitats Directive, which suggests the use of typical species to assess habitat conservation status. Yet, the Directive uses the term “typical” species but does not provide a definition, either for its use in reporting or for its use in impact assessments. To address the issue, an online workshop was organized by the Italian Society for Vegetation Science (SISV) to shed light on the diversity of perspectives regarding the different concepts of typical species, and to discuss the possible implications for habitat monitoring. To this aim, we inquired 73 people with a very different degree of expertise in the field of vegetation science by means of a tailored survey composed of six questions. We analysed the data using Pearson's Chi-squared test to verify that the answers diverged from a random distribution and checked the effect of the degree of experience of the surveyees on the results. We found that most of the surveyees agreed on the use of the phytosociological method for habitat monitoring and of the diagnostic and characteristic species to evaluate the structural and functional conservation status of habitats. With this contribution, we shed light on the meaning of “typical” species in the context of habitat monitoring

Adjuvant capecitabine in triple negative breast cancer patients with residual disease after neoadjuvant treatment: real-world evidence from CaRe, a multicentric, observational study

Background: In triple negative breast cancer patients treated with neoadjuvant chemotherapy, residual disease at surgery is the most relevant unfavorable prognostic factor. Current guidelines consider the use of adjuvant capecitabine, based on the results of the randomized CREATE-X study, carried out in Asian patients and including a small subset of triple negative tumors. Thus far, evidence on Caucasian patients is limited, and no real-world data are available. Methods: We carried out a multicenter, observational study, involving 44 oncologic centres. Triple negative breast cancer patients with residual disease, treated with adjuvant capecitabine from January 2017 through June 2021, were recruited. We primarily focused on treatment tolerability, with toxicity being reported as potential cause of treatment discontinuation. Secondarily, we assessed effectiveness in the overall study population and in a subset having a minimum follow-up of 2 years. Results: Overall, 270 patients were retrospectively identified. The 50.4% of the patients had residual node positive disease, 7.8% and 81.9% had large or G3 residual tumor, respectively, and 80.4% a Ki-67 >20%. Toxicity-related treatment discontinuation was observed only in 10.4% of the patients. In the whole population, at a median follow-up of 15 months, 2-year disease-free survival was 62%, 2 and 3-year overall survival 84.0% and 76.2%, respectively. In 129 patients with a median follow-up of 25 months, 2-year disease-free survival was 43.4%, 2 and 3-year overall survival 78.0% and 70.8%, respectively. Six or more cycles of capecitabine were associated with more favourable outcomes compared with less than six cycles. Conclusion: The CaRe study shows an unexpectedly good tolerance of adjuvant capecitabine in a real-world setting, although effectiveness appears to be lower than that observed in the CREATE-X study. Methodological differences between the two studies impose significant limits to comparability concerning effectiveness, and strongly invite further research

Multi-pathway blood biomarkers to target and monitor multidimensional prevention of cognitive and functional decline (nested in the IN-TeMPO study framed within the world-wide FINGERS network)

BackgroundAs the population ages, the identification of preventive strategies able to delay cognitive and functional decline associated with aging represents a major challenge. To date, multidimensional approaches seem to be effective in reducing or delaying the onset of age-related diseases.ObjectivesThe multicentric randomized controlled trial IN-TeMPO (ItaliaN study with Tailored Multidomain interventions to Prevent functional and cognitive decline in community-dwelling Older adults, ClinicalTrials.gov ID NCT06248723), framed within the World-Wide FINGERS network, aims to verify the efficacy of guided multidomain interventions in preventing age-related cognitive and functional decline. Within this study, we will explore a comprehensive array of established and exploratory blood biomarkers of several pathologic age-related processes, including Alzheimer’s disease (AD), neurodegeneration, inflammation, senescence and sarcopenia, to stratify subject risk and assess the effect of multidomain interventions on biomarkers.Design and participantsApoE4 status and plasma p-tau217 (AD), NfL (neurodegeneration), GFAP and IL-6 (inflammation), GDF-15 (senescence/sarcopenia) will be evaluated in all subjects (n = 1,662) both at the baseline and at the end of the study (12 months). Exploratory additional biomarkers will be measured at the same time points in a subgroup of 100 subjects: BDNF, ghrelin, IGF-1, irisin and redox status in plasma as markers of sarcopenia/senescence and oxidative stress, gamma-H2AX in PBMCs as marker of senescence, and amyloid beta aggregates in plasma, urine and erythrocytes as supportive markers of AD. Untargeted metabolomics analysis in plasma and untargeted volatilomics analysis in whole blood and urine will be performed to explore molecular alterations that may be associated with the pathogenesis and progression of age-related diseases in frail older adults with the aim of identifying novel potential biomarkers.ConclusionThe comprehensive clinical use of multiple laboratory biomarkers can contribute both to the early identification of trajectories of cognitive and functional decline in older adults, and to the identification of mechanisms underlying the effect of multidisciplinary interventions on age-related pathological processes