Bio-Polyethylene-Based Composites Reinforced with Alkali and Palmitoyl Chloride-Treated Coffee Silverskin

[EN] This work investigates the feasibility of using coffee silverskin (CSS) as a reinforcing agent in biobased polyethylene (BioPE) composites, by adding it in bulk and thin film samples. The effect of two different treatments, alkali bleaching (CSS_A) and esterification with palmitoyl chloride (CSS_P), on mechanical, thermal, morphological and water absorption behavior of produced materials at different CSS loading (10, 20 and 30 wt %) was investigated. A reactive graft copolymerization of BioPE with maleic anhydride was considered in the case of alkali treated CSS. It was found that, when introduced in bulk samples, improvement in the elastic modulus and a reduction in strain at maximum stress were observed with the increase in CSS fraction for the untreated and treated CSS composites, while the low aspect ratio of the CSS particles and their poor adhesion with the polymeric matrix were responsible for reduced ductility in films, decreasing crystallinity values and reduction of elastic moduli. When CSS_A and CSS_P are introduced in the matrix, a substantial reduction in the water uptake is also obtained in films, mainly due to presence of maleated PE, that builds up some interactions to eliminate the amounts of OH groups and hydrophobized CSS, due to the weakened absorption capacity of the functionalized CSS.This research was partially funded by the Ministry of Science, Innovation, and Universities (MICIU) project number MAT2017-84909-C2-2-R. D.G.G. wants to thank the Universitat Politècnica de València for financial support through a postdoctoral contract [PAID-10-18].Dominici, F.; Garcia-Garcia, D.; Fombuena, V.; Luzi, F.; Puglia, D.; Torre, L.; Balart, R. (2019). Bio-Polyethylene-Based Composites Reinforced with Alkali and Palmitoyl Chloride-Treated Coffee Silverskin. Molecules. 24(17):1-14. https://doi.org/10.3390/molecules24173113S1142417Carbonell-Verdú, A., García-García, D., Jordá, A., Samper, M. D., & Balart, R. (2015). Development of slate fiber reinforced high density polyethylene composites for injection molding. Composites Part B: Engineering, 69, 460-466. doi:10.1016/j.compositesb.2014.10.026Zhang, H. (2014). Effect of a novel coupling agent, alkyl ketene dimer, on the mechanical properties of wood–plastic composites. Materials & Design, 59, 130-134. doi:10.1016/j.matdes.2014.02.048Garcia-Garcia, D., Carbonell-Verdu, A., Jordá-Vilaplana, A., Balart, R., & Garcia-Sanoguera, D. (2016). 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Design and Characterization of PLA Bilayer Films Containing Lignin and Cellulose Nanostructures in Combination With Umbelliferone as Active Ingredient

Poly (lactic acid) (PLA) bilayer films, containing cellulose nanocrystals (CNC) or lignin nanoparticles (LNP) and Umbelliferone (UMB) were extruded and successfully layered by thermo-compression starting from monolayer films. Lignocellulosic nanostructures were used in PLA based film as nanofillers at 3 wt.%, while UMB was used as active ingredient (AI) at 15 wt.%. The effects of processing techniques, presence, typology and content of lignocellulosic nanoparticles have been analyzed and thermal, morphological, mechanical and optical characterization of PLA nanocomposites have been made.Furthermore, X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FTIR) studies evaluated the presence of nanofillers and AI at chemical level. Bilayer formulations showed a good interfacial adhesion and improved stress at break with respect of PLA monolayers, although they were less stretchable and transparent. Data obtained from thermal, colorimetric and transparency investigations underlined that the presence of lignocellulosic nanofillers and AI in PLA monolayer and bilayer films induced relevant alterations in terms of overall color properties and thermal stability, while antioxidant activity of umbelliferone was enhanced by the addition of lignin in produced materials.Fil: Iglesias Montes, Magdalena Luz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Luzi, Francesca. Università di Perugia; ItaliaFil: Dominici, Franco. Università di Perugia; ItaliaFil: Torre, Luigi. Università di Perugia; ItaliaFil: Cyras, Viviana Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Manfredi, Liliana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Puglia, Debora. Università di Perugia; Itali

Synergic Effect of Nanolignin and Metal Oxide Nanoparticles into Poly(l-lactide) Bionanocomposites: Material Properties, Antioxidant Activity, and Antibacterial Performance

Binary and ternary poly (L-lactide) (PLLA) based nanocomposites, containing nanolignin (1% wt.) and different metal oxide nanoparticles (0.5% wt., Ag2O, TiO2, WO3, Fe2O3 and ZnFe2O4) were realized ..

Effect of Chlorophyll Hybrid Nanopigments from Broccoli Waste on Thermomechanical and Colour Behaviour of Polyester-Based Bionanocomposites

[EN] Natural dyes obtained from agro-food waste can be considered promising substitutes of synthetic dyes to be used in several applications. With this aim, in the present work, we studied the use of chlorophyll dye (CD) extracted from broccoli waste to obtain hybrid nanopigments based on calcined hydrotalcite (HT) and montmorillonite (MMT) nanoclays. The synthesized chlorophyll hybrid nanopigments (CDNPs), optimized by using statistical designed experiments, were melt-extruded with a polyester-based matrix (INZEA) at 7 wt% loading. Mechanical, thermal, structural, morphological and colour properties of the obtained bionanocomposites were evaluated. The obtained results evidenced that the maximum CD adsorption into HT was obtained when adding 5 wt% of surfactant (sodium dodecyl sulphate) without using any biomordant and coupling agent, while the optimal conditions for MMT were achieved without adding any of the studied modifiers. In both cases, an improvement in CD thermal stability was observed by its incorporation in the nanoclays, able to protect chlorophyll degradation. The addition of MMT to INZEA resulted in large Delta E* values compared to HT incorporation, showing bionanocomposite green/yellow tones as a consequence of the CDNPs addition. The results obtained by XRD and TEM revealed a partially intercalated/exfoliated structure for INZEA-based bionanocomposites, due to the presence of an inorganic filler in the formulation of the commercial product, which was also confirmed by TGA analysis. CDNPs showed a reinforcement effect due to the presence of the hybrid nanopigments and up to 26% improvement in Young's modulus compared to neat INZEA. Finally, the incorporation of CDNPs induced a decrease in thermal stability as well as limited effect in the melting/crystallization behaviour of the INZEA matrix. The obtained results showed the potential use of green natural dyes from broccoli wastes, adsorbed into nanoclays, for the development of naturally coloured bionanocomposites.The authors express their gratitude to the Bio Based Industries Consortium and European Commission for the financial support to the project BARBARA: Biopolymers with advanced functionalities for building and automotive parts processed through additive manufacturing. This project received funding from the Bio Based Industries Joint Undertaking under the European Union's Horizon 2020 research and innovation programme under grant agreement No 745578.Micó-Vicent, B.; Ramos, M.; Luzi, F.; Dominici, F.; Viqueira, V.; Torre, L.; Jiménez, A.... (2020). Effect of Chlorophyll Hybrid Nanopigments from Broccoli Waste on Thermomechanical and Colour Behaviour of Polyester-Based Bionanocomposites. Polymers. 12(11):1-19. https://doi.org/10.3390/polym12112508S119121

Evaluation of the Factors Affecting the Disintegration under a Composting Process of Poly(lactic acid)/Poly(3-hydroxybutyrate) (PLA/PHB) Blends

The overall migration behavior and the disintegration under composting conditions of films based on plasticized poly(lactic acid)/poly(3-hydroxybutyrate) (PLA-PHB) blends were studied, with the main aim of determining the feasibility of their application as biodegradable food packaging materials. The role of composition in the disintegration process was evaluated by monitoring the changes in physical and thermal properties that originated during the degradation process. PLA and PHB were blended in two weight ratios with 15 wt% of tributyrin, using a Haake mixer and then compression molded into ~150 µm films. We found that the migration level of all of the studied blends was below check intended meaning retained in non-polar simulants, while only plasticized blends could withstand the contact with polar solvents. The disintegration of all of the materials in compost at 58 ◦C was completed within 42 days; the plasticized PHB underwent the fastest degradation, taking only 14 days. The presence of the TB plasticizer speeded up the degradation process. Different degradation mechanisms were identified for PLA and PHB. To evaluate the annealing effect separately from bacteria degradation, the influence of temperature on materials in the absence of a compost environment was also studied. With the increasing time of degradation in compost, both melting temperature and maximum degradation temperature progressively decreased, while the crystallinity degree increased, indicating that the samples were definitely degrading and that the amorphous regions were preferentially eroded by bacteria.Fil: Iglesias Montes, Magdalena Luz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Soccio, Michelina. Università di Bologna; ItaliaFil: Luzi, Francesca. Università di Perugia; ItaliaFil: Puglia, Debora. Università di Perugia; ItaliaFil: Gazzano, Massimo. National Research Council; ItaliaFil: Lotti, Nadia. Università di Bologna; ItaliaFil: Manfredi, Liliana Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; ArgentinaFil: Cyras, Viviana Paola. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones en Ciencia y Tecnología de Materiales. Universidad Nacional de Mar del Plata. Facultad de Ingeniería. Instituto de Investigaciones en Ciencia y Tecnología de Materiales; Argentin

Effect of Lemon Waste Natural Dye and Essential Oil Loaded into Laminar Nanoclays on Thermomechanical and Color Properties of Polyester Based Bionanocomposites

[EN] In this work, polyester-based nanocomposites added with laminar nanoclays (calcined hydrotalcite, HT, and montmorillonite, MMT) loaded with lemon waste natural dye (LD) and essential oil (LEO) were prepared and characterized. The optimal conditions to synthetize the hybrid materials were obtained by using statistically designed experiments. The maximum LD adsorption with HT was found using 5 wt% of surfactant (sodium dodecyl sulfate), 5 wt% of mordant (aluminum potassium sulfate dodecahydrate) and 50% (v/v) ethanol. For MMT, 10 wt% of surfactant (cetylpyridinium bromide), 5 wt% of mordant, 1 wt% of (3-aminopropyl) triethoxysilane and 100% distilled water were used. LEO adsorption at 300 wt% was maximized with MMT, 10 wt% of surfactant and 50 degrees C following an evaporation/adsorption process. The obtained hybrid nanofillers were incorporated in a polyester-based matrix (INZEA) at different loadings (3, 5, and 7 wt%) and the obtained samples were characterized in terms of thermal stability, tensile behavior, and color properties. HT_LEM-based samples showed a bright yellow color compared to MMT_LEM ones. The presence of lemon hybrid pigments in INZEA-based systems produced a remarkable variation in CIELAB color space values, which was more visible with increasing the nanofillers ratio. A limited mechanical enhancement and reduced thermal stability was observed with the nanopigments addition, suggesting a limited extent of intercalation/exfoliation of MMT and HT in the polymer matrix. MMT_LEM pigments showed higher thermal stability than HT_LEM ones. A significant increase in Young's modulus of nanocomposites loaded with hybrid LEO was observed compared to the biopolymer matrix. The LEO inclusion into the nanoclays efficiently improved its thermal stability, especially for MMT.The authors express their gratitude to the Bio Based Industries Consortium and European Commission for the financial support to the project BARBARA: Biopolymers with advanced functionalities for building and automotive parts processed through additive manufacturing. This project has received funding from the Bio Based Industries Joint Undertaking under the European Union's Horizon 2020 research and innovation programme under grant agreement No 745578.Micó-Vicent, B.; Viqueira, V.; Ramos, M.; Luzi, F.; Dominici, F.; Torre, L.; Jiménez, A.... (2020). Effect of Lemon Waste Natural Dye and Essential Oil Loaded into Laminar Nanoclays on Thermomechanical and Color Properties of Polyester Based Bionanocomposites. Polymers. 12(7):1-22. https://doi.org/10.3390/polym12071451S12212

Anthocyanin Hybrid Nanopigments from Pomegranate Waste: Colour, Thermomechanical Stability and Environmental Impact of Polyester-Based Bionanocomposites

In the present work, anthocyanin (ACN) hybrid nanopigments were synthetized by using a natural pomegranate dye (PD) and calcined hydrotalcite (HT) and montmorillonite (MMT) nanoclays. A wide colour gamut was obtained with MMT-based nanopigments ranging from reddish to bluish hues caused by structural transformations of ACNs at different pH values. However, a buffer effect was observed with HT obtaining samples a similar final colour regardless of the synthesis conditions. Nanopigments added with a biomordant extracted from pomegranate peels showed a different colour compared to the incorporation of a commercial mordant due to the intrinsic colouring properties of the pomegranate bioadditive. The developed nanopigments were incorporated at 7 wt% loading to produce novel polyester-based bionanocomposites which were characterized in terms of thermal, mechanical and colour properties. The encapsulation of PD into the nanoclays improved its thermal stability, in particular for MMT-based nanopigments. The pH changes observed during the nanofillers synthesis affected the final colour of the MMT-based nanocomposites, inducing a general increase in ∆E* and a decrease in gloss values. Slight improvements were obtained in terms of elastic modulus for MMT-based polymer samples confirming the applicability of the developed bionanocomposites as colouring and reinforcement materials. A very similar environmental profile was obtained for MMT and HT-based nanofillers showing MMT-based nanopigments a slightly better general behaviour. The results of the LCA study evidenced the suitability of the processes used in this work to the circular bioeconomy approach through sustainable food waste management and the production of bioplastics using waste substrates.This project has received funding from the Bio Based Industries Joint Undertaking under the European Union’s Horizon 2020 research and innovation programme under grant agreement No 745578

Low low-density lipoprotein (LDL), cholesterol and triglycerides plasma levels are associated with reduced risk of arterial occlusive events in chronic myeloid leukemia patients treated with ponatinib in the real-life. A Campus CML study

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Determinants of frontline tyrosine kinase inhibitor choice for patients with chronic-phase chronic myeloid leukemia: A study from the Registro Italiano LMC and Campus CML

Background: Imatinib, dasatinib, and nilotinib are tyrosine kinase inhibitors (TKIs) approved in Italy for frontline treatment of chronic-phase chronic myeloid leukemia (CP-CML). The choice of TKI is based on a combined evaluation of the patient's and the disease characteristics. The aim of this study was to analyze the use of frontline TKI therapy in an unselected cohort of Italian patients with CP-CML to correlate the choice with the patient's features. Methods: A total of 1967 patients with CP-CML diagnosed between 2012 and 2019 at 36 centers throughout Italy were retrospectively evaluated; 1089 patients (55.4%) received imatinib and 878 patients (44.6%) received a second-generation (2G) TKI. Results: Second-generation TKIs were chosen for most patients aged <45 years (69.2%), whereas imatinib was used in 76.7% of patients aged >65 years (p < .001). There was a predominant use of imatinib in intermediate/high European long-term survival risk patients (60.0%/66.0% vs. 49.7% in low-risk patients) and a limited use of 2G-TKIs in patients with comorbidities such as hypertension, diabetes, chronic obstructive pulmonary disease, previous neoplasms, ischemic heart disease, or stroke and in those with >3 concomitant drugs. We observed a greater use of imatinib (61.1%) in patients diagnosed in 2018-2019 compared to 2012-2017 (53.2%; p = .002). In multivariable analysis, factors correlated with imatinib use were age > 65 years, spleen size, the presence of comorbidities, and ≥3 concomitant medications. Conclusions: This observational study of almost 2000 cases of CML shows that imatinib is the frontline drug of choice in 55% of Italian patients with CP-CML, with 2G-TKIs prevalently used in younger patients and in those with no concomitant clinical conditions. Introduction of the generic formulation in 2018 seems to have fostered imatinib use

Analysis of Early Events during the First Year of Tyrosine Kinase Inhibitor Therapy in Patients with Chronic Phase - Chronic Myeloid Leukemia: A "Campus CML" Study

Tyrosine kinase inhibitors (TKIs) revolutionized treatment of chronic myeloid leukemia (CML). However, the rst months of therapy are crucial, as optimal response is dened as the achievement of molecular milestones at 3, 6 and 12 months (mo.) and as many toxicities, also causing a TKI switch, are more frequent in the 1st yea