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

Synthesis and Properties of an Electropolymer Obtained from a Dimeric Donor/Acceptor System with a 4,4′-Spirobi[cyclopenta[2,1-b:3,4-b′]dithiophene] Core

The design and synthesis of two potentially electropolymerizable electron donor-acceptor dyes characterized by a cruciform 4,4′-spirobi[cyclopenta[2,1-b:3,4-b′]dithiophene] core is here outlined. The new molecules feature two perpendicularly aligned cyclopentadithiophene branches, each one having an electrodimerizable, electron donor triphenylamine unit and an electron acceptor dicyanovinylene group. By merging these structural elements, the light absorption ability of the conjugated cyclopentadithiophene chromophore is extended to a broad region of the visible spectrum. The photoelectroactive film obtained from one of the dyes by electrochemical deposition technique retains the ability to generate photoinduced charge-separated states and to transport holes, turning this material into a unique example of donor-acceptor polymer with potential application in the development of organic optoelectronic devices. (Figure Presented).Fil: Orlandi, Simonetta. Instituto di Scienze e Tecnologie Molecolari del Consiglio Nazionale delle Ricerche; ItaliaFil: Pozzi, Gianluca. Instituto di Scienze e Tecnologie Molecolari del Consiglio Nazionale delle Ricerche; ItaliaFil: Cavazzini, Marco. Instituto di Scienze e Tecnologie Molecolari del Consiglio Nazionale delle Ricerche; ItaliaFil: Minudri, Daniela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Gervaldo, Miguel Andres. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Otero, Luis Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; ArgentinaFil: Fungo, Fernando Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentin

Valutazione iniziale dell’impiego del sistema Da Vinci nella surrenectomia robotica

Introduction: In last years we have witnessed a progressive expansion of robotic abdominal surgery. The aim of our preliminary study was to determine potential advantages and limitations in adrenalectomy procedure. Methods: We prospectively evaluated five consecutive cases of monolateral transperitoneal robotic adrenalectomy. All the procedures were performed with the Da Vinci S surgical system, with the patient in 45° lateral decubitus, opposite to the lesion site, and with a 20° antitrendelemburg. Two robotic trocars were inserted into the flank and into the iliac fossa omolaterally plus a third trocar positioned in the controlateral hypochondrium for the assistant surgeon at the operating table. Results: From May 2007 until March 2009 at the European Institute of Oncology has been performed five adrenalectomy procedures, with full robotic technique. Two patients were male and three female. Mean age was 62.4 ± 11.3 years. Three were left and two were right adrenalectomies. Histology was: two adrenocortical adenomas and three metastasis, one from melanoma, one from ovarian cancer and the last from lung cancer. Mean operative time was 178 ± 28 min. with no conversion to open technique. Mean post-operative hospital stay was 4.4 ± 1.6 days (range 2-6) and none had post-operative minor or major complications. Blood loss was negligible in all cases. Conclusions: Robotic adrenalectomy have subjective advantages as the better identification of the dissection planes, thanks to the magnified vision of the operative field and the easier and safer isolation of the delicate anatomical structures with this type of surgery. An objective superiority of this technique over the traditional ones should be demonstrated with further studies

Emicolectomia destra completamente robotica: analisi dei risultati clinici e oncologici precoci

Clinical and oncological results of routine application of robotic right hemicolectomy has been evaluated. Data from 14 consecutive patients, affected by right colon cancer, were prospectively collected and evaluated. The Authors suggest that superior dexterity of robotic instruments and tridimensional magnified vision of the operative field allow a subjective better identification and a safer isolation of the anatomical structures, although no relevant advantage over standard laparoscopy was found in their preliminary experience

Resezione anteriore del retto completamente robotica: tecnica e risultati oncologici preliminari

Introduzione: La tecnica di resezione anteriore del retto robotica con escissione completa del mesoretto non è ancora standardizzata. Molti autori, infatti, preferiscono adottare una tecnica ibrida che prevede l’utilizzo della laparoscopia convenzionale per la legatura dei vasi e per la mobilizzazione della flessura splenica. Presentiamo una tecnica che permette di eseguire quest’intervento in maniera completamente robotica e avvalendosi di un unico posizionamento del carrello robotico. Metodi: Tutti gli interventi sono stati eseguiti utilizzando un unico posizionamento del carrello robotico. Per tutte le procedure sono stati impiegati tre bracci robotici più un ulteriore trocar per l’assistente posto al tavolo operatorio. I dati ottenuti sono stati raccolti prospetticamente in un database dedicato e analizzati. Risultati: Da gennaio 2007 a marzo 2009 presso la Divisione di Chirurgia Addomino-Pelvica dell’Istituto Europeo di Oncologia di Milano sono state operati 47 pazienti affetti da cancro del retto con tecnica completamente robotica impiegando il robot Da Vinci S: 19 femmine e 28 maschi. L’età media è stata di 62.4 ± 10.3 anni (range 37-82). Procedure in dettaglio: 32 resezioni anteriori del retto, 7 resezioni intersfinteriche e 8 addomino-perineali. Il tempo operatorio medio è stato di 300 ± 69 min (range 156-487). Nessun paziente è stato convertito in chirurgia open. Il numero di linfonodi asportati è stato in media 17.6 ± 7.2 (range 5-39), la distanza dal margine di resezione distale è stata in media di 26,14 ± 13 mm e il margine circonferenziale è risultato negativo in tutti i casi. Conclusioni: La resezione anteriore del retto completamente robotica eseguita con questa tecnica è una procedura oncologicamente sicura ed efficace nel trattamento delle neoplasie del retto. Essa sfrutta i vantaggi della chirurgia robotica in ogni fase dell’intervento senza la necessità di utilizzare tecniche ibride