A Perspective on Recent Advances in Phosphorene Functionalization and its Application in Devices

Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in material science. In particular, the physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in preparation, functionalization and use of phosphorene and its decorated derivatives. In particular, we discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behaviour of black phosphorus, as well as decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and new results collected in our laboratories

Polymer-based black phosphorus (bP) hybrid materials by in situ radical polymerization: an effective tool to exfoliate bP and stabilize bP nanoflakes

Black phosphorus (bP) has been recently investigated for next generation nanoelectronic multifunctional devices. However, the intrinsic instability of exfoliated bP (the bP nanoflakes) towards both moisture and air has so far overshadowed its practical implementation. In order to contribute to fill this gap, we report here the preparation of new hybrid polymer-based materials where bP nanoflakes exhibit a significantly improved stability. The new materials have been prepared by different synthetic paths including: i) the mixing of conventionally liquid-phase exfoliated bP (in DMSO) with PMMA solution; ii) the direct exfoliation of bP in a polymeric solution; iii) the in situ radical polymerization after exfoliating bP in the liquid monomer (methyl methacrylate, MMA). This last methodology concerns the preparation of stable suspensions of bPn-MMA by sonication-assisted liquid phase exfoliation (LPE) of bP in the presence of MMA followed by radical polymerization. The hybrids characteristics have been compared in order to evaluate the bP dispersion and the effectiveness of the bPn interfacial interactions with polymer chains aimed at their long-term environmental stabilization. The passivation of bPn results particularly effective when the hybrid material is prepared by in situ polymerization. By using this synthetic methodology, the nanoflakes, even if with a gradient of dispersion (size of aggregates), preserve their chemical structure from oxidation (as proved by both Raman and 31P-Solid State NMR studies) and are particularly stable to air and UV light exposure

Characteristics and patterns of care of endometrial cancer before and during COVID-19 pandemic

Objective: Coronavirus disease 2019 (COVID-19) outbreak has correlated with the disruption of screening activities and diagnostic assessments. Endometrial cancer (EC) is one of the most common gynecological malignancies and it is often detected at an early stage, because it frequently produces symptoms. Here, we aim to investigate the impact of COVID-19 outbreak on patterns of presentation and treatment of EC patients. Methods: This is a retrospective study involving 54 centers in Italy. We evaluated patterns of presentation and treatment of EC patients before (period 1: March 1, 2019 to February 29, 2020) and during (period 2: April 1, 2020 to March 31, 2021) the COVID-19 outbreak. Results: Medical records of 5,164 EC patients have been retrieved: 2,718 and 2,446 women treated in period 1 and period 2, respectively. Surgery was the mainstay of treatment in both periods (p=0.356). Nodal assessment was omitted in 689 (27.3%) and 484 (21.2%) patients treated in period 1 and 2, respectively (p<0.001). While, the prevalence of patients undergoing sentinel node mapping (with or without backup lymphadenectomy) has increased during the COVID-19 pandemic (46.7% in period 1 vs. 52.8% in period 2; p<0.001). Overall, 1,280 (50.4%) and 1,021 (44.7%) patients had no adjuvant therapy in period 1 and 2, respectively (p<0.001). Adjuvant therapy use has increased during COVID-19 pandemic (p<0.001). Conclusion: Our data suggest that the COVID-19 pandemic had a significant impact on the characteristics and patterns of care of EC patients. These findings highlight the need to implement healthcare services during the pandemic

Co-agent mediated functionalization of LDPE/iPP mixtures for compatibilization of WEEE-recovered polyvinylchloride

Mixtures of low density polyethylene/isotactic polypropylene (LDPE/iPP) 80/20 w/w were functionalized in the melt by using maleic anhydride (MAH) as the functionalizing agent, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (L101) as the peroxide initiator and butyl 3-(2-furyl)propenoate (BFA) as a co-agent suitable to prevent the degradation of iPP and to promote inter-macromolecular reactions. The use of BFA was aimed at favouring the control of radical-induced side reactions and the formation of interfacial graft copolymers. The functionalization degree and the modification of macromolecular architecture, which were evaluated by selective solvent extractions combined with IR, DSC and SEM analyses, were modulated by varying the L101/MAH/BFA ratio in the feed. The optimized product in terms of functionalization degree value and processability was successfully tested as compatibilizer in a polyolefin/polyvinylchloride mixture, where the polyvinylchloride component resulted from the management of waste of electrical and electronic equipment (WEEE)

Rosmarinic acid and Ulvan from terrestrial and marine sources in anti-microbial bionanosystems and biomaterials

In order to increase their sustainability, antimicrobial renewable molecules are fundamen-tal additions to consumer goods. Rosmarinic acid is extracted from several terrestrial plants and represents an effective anti-microbial agent. Ulvan, extracted from algae, is an anti-microbial poly-saccharide. The present review is dedicated to discussing the sources and the extraction methodologies for obtaining rosmarinic acid and ulvan. Moreover, the preparation of bioanosystems, inte-grating the two molecules with organic or inorganic substrates, are reviewed as methodologies to increase their effectiveness and stability. Finally, the possibility of preparing functional biomaterials and anti-microbial final products is discussed, considering scientific literature. The performed analysis indicated that the production of both molecules is not yet performed with mature industrial technologies. Nevertheless, both molecules could potentially be used in the packaging, biomedical, pharmaceutical, cosmetic, sanitary and personal care sectors, despite some research being required for developing functional materials with specific properties to pave the way for many more applications

Rosmarinic Acid and Ulvan from Terrestrial and Marine Sources in Anti-Microbial Bionanosystems and Biomaterials

In order to increase their sustainability, antimicrobial renewable molecules are fundamental additions to consumer goods. Rosmarinic acid is extracted from several terrestrial plants and represents an effective anti-microbial agent. Ulvan, extracted from algae, is an anti-microbial polysaccharide. The present review is dedicated to discussing the sources and the extraction methodologies for obtaining rosmarinic acid and ulvan. Moreover, the preparation of bioanosystems, integrating the two molecules with organic or inorganic substrates, are reviewed as methodologies to increase their effectiveness and stability. Finally, the possibility of preparing functional biomaterials and anti-microbial final products is discussed, considering scientific literature. The performed analysis indicated that the production of both molecules is not yet performed with mature industrial technologies. Nevertheless, both molecules could potentially be used in the packaging, biomedical, pharmaceutical, cosmetic, sanitary and personal care sectors, despite some research being required for developing functional materials with specific properties to pave the way for many more applications

Fluorescent LDPE and PLA nanocomposites containing fluorescein-modified layered double hydroxides and their ON/OFF responsive behavior towards humidity

We report on the preparation and characterization of fluorescent polymer nanocomposites based upon poly(lactic acid) (PLA) or linear low density polyethylene (LDPE) filled with 5 wt% of fluorescein-modified layered nanoparticles. Modified layered double hydroxide (LDH) nanoparticles were prepared by co-intercalation of fluorescein and alkyl sulfate anions thus yielding to three hybrid samples having different lambda of emission and quantum yield, depending on fluorophore content and presence of dye aggregates. Further separation of Flu aggregates by dispersion of less fluorescent co-intercalated LDHs in PLA and LDPE resulted in an increase of the quantum yield, with better results for PLA-based nanocomposites in agreement with a better morphology. Preliminary data indicated the possible use of these materials as ON/OFF humidity indicators

Poly(lactic acid) plasticized with low-molecular-weight polyesters: structural, thermal and biodegradability features

Poly(lactic acid) (PLA) was plasticized with ester oligomers having different structure, molecular weight and carboxylic acid content as end-functionalities. In particular PLA oligomers and a low-molecular-weight polyester of adipic acid and 1,2-propanediol (an adipate-based derivative) were used and compared. The plasticizing capability was tested and the final structural and thermal properties of PLA matrix were evaluated by correlating the various features to the chemical and physical characteristics of these additives. SEC, DSC, TGA, tensile tests, XRD and SEM results, even after annealing, were collected, and the related data analysed and evaluated with reference to additive starting properties. All the oligoesters were able to generate flexible compounds, but PLA oligomers provided mixtures with reduced structural and thermal stability. Finally, the best performing blend was tested for biodegradability to definitely assess the material suitability for the final application (sustainable packaging). © 2017 Society of Chemical Industry