Chitosan–Chitin Nanocrystal Films from Lobster and Spider Crab: Properties and Environmental Sustainability

The valorization of chitinous biomass from underutilized renewable carbon feedstock offers alternative routes for bioproduct development, reducing our dependence on nonrenewable and nonbiodegradable materials composed of fossil carbon. This work utilizes crustacean waste consisting of inedible shells to isolate chitin and its derivatives, chitin nanocrystals and chitosan, from lobster (Homarus gammarus) and spider crab (Maja squinado) shells. Chitin nanocrystals (ChNCs) with a degree of acetylation >93% and crystallinity >90% were obtained by demineralization, deproteinization and acid-hydrolysis, while chitosan was obtained by chitin deacetylation. Free-standing chitosan/ChNCs films were then fabricated from lobster and spider crab after dissolution and casting using 1.5% v/v formic acid. Lobster-derived materials exhibited a good balance between UV-shielding ability, blocking >96% of UV-C and UV-B, while being transparent at visible wavelengths. Neat chitosan films are semiductile, with elongations at break >13% and Young’s modulus values of 2.3 ± 0.7 and 3.4 ± 1.2 GPa for lobster and spider crab-derived chitosan, respectively. Besides, the incorporation of ChNCs increases the Young’s modulus to 5.5 ± 0.8 GPa at 2 wt % for lobster-derived films. Life cycle assessment (LCA) was conducted to quantify the environmental impact of film production and identify process hotspots for future optimization. A carbon footprint of 79.8 kg CO2 equiv·kg–1 is obtained for chitosan/ChNC films processed using a 100% renewable energy mix. Results demonstrate that lobster-derived materials are relevant contenders toward defossilization by developing renewable-carbon containing bioproducts with competitive performance against fossil-based materials due to their optical and mechanical properties, as well as their potential biodegradability.Financial support from the “2021 Euskampus Missions 1.0. Programme” granted by Euskampus Fundazioa is acknowledged. The authors are thankful for funds from the University of the Basque Country (GIU21/010)

Microwave-Assisted Extraction of Curcuma longa L. Oil: Optimization, Chemical Structure and Composition, Antioxidant Activity and Comparison with Conventional Soxhlet Extraction

Curcuma root (Curcuma longa L.) is a very important plant in gastronomy and medicine for its unique antiseptic, anti-inflammatory, antimicrobial and antioxidant properties. Conventional methods for the extraction of curcuma oil require long extraction times and high temperatures that can degrade the active substances. Therefore, the objectives of the present study were: (i) first, to optimize the extraction yield of curcuma oil by applying a Box-Behnken experimental design using surface response methodology to the microwave-assisted extraction (MAE) technique (the independent variables studied were reaction time (10–30 min), microwave power (150–200 W) and curcuma powder/ethanol ratio (1:5–1:20; w/v); and, (ii) second, to assess the total phenolic content (TPC) and their antioxidant activity of the oil (at the optimum conditions point) and compare with the conventional Soxhlet technique. The optimum conditions for the MAE were found to be 29.99 min, 160 W and 1:20 w/v to obtain an optimum yield of 10.32%. Interestingly, the oil extracted by microwave-assisted extraction showed higher TPC and better antioxidant properties than the oil extracted with conventional Soxhlet technique. Thus, it was demonstrated that the method applied for extraction influences the final properties of the extracted Curcuma longa L. oil.This research was funded by the Basque Country Government (IT 1008-16)

Halochromic and antioxidant capacity of smart films of chitosan/chitin nanocrystals with curcuma oil and anthocyanins

Curcuma longa L. essential oil and anthocyanin extracts contain bioactive compounds such as antioxidant properties and their pigments are able to change color when exposed to different pH or ammonium gas. In this context, the objective of the present work was to develop pH-sensitive intelligent films by adding curcuma oil (composed of essential oils and pigments) and anthocyanin extracts to a chitosan matrix reinforced with alphachitin nanocrystals. The incorporation of curcuma oil, anthocyanins and nanocrystals enhanced the mechanical properties and hydrophobicity; and, decreased water solubility and moisture content. In addition, the films also showed almost total blocking against UV/Vis light at wavelengths below 550 nm. Interestingly, the films were at the same time antioxidant, and sensitive to color change when exposed to ammonia gas and different pH solutions, with greater variations observed when higher concentrations of curcuma oil were added. Hence, these results revealed the potential of these films as intelligent food packaging applications.The authors would like to thank the funding from the Basque Country Government (IT 1008-16). R. F. -M. acknowledge the financial support of the Basque Country Government (scholarship of young researchers training). S.C.M.F. is a recipient of an E2S UPPA MANTA E2S Partnership Chair (Marine Materials) sponsored by the French programme "Investissements d'Avenir" administered by the French National Research Agency (ANR-16-IDEX-IDEX). The authors wish to acknowledge the technical and human assistance received from SGIker (UPV/EHU/ERDF, EU), Spain

Understanding the effects of copolymerized cellulose nanofibers and diatomite nanocomposite on blend chitosan films

Chitosan films lack various important physicochemical properties and need to be supplemented with reinforcing agents to bridge the gap. Herein, we have produced chitosan composite films supplemented with copolymerized (with polyacrylonitrile monomers) cellulose nanofibers and diatomite nanocomposite at different concentrations. The incorporation of CNFs and diatomite enhanced the physicochemical properties of the films. The mechanical characteristics and hydrophobicity of the films were observed to be improved after incorporating the copolymerized CNFs/diatomite composite at different concentrations (CNFs: 1%, 2% and 5%; diatomite: 10% and 30%). The antioxidant activity gradually increased with an increasing concentration (1-5% and 10-30%) of copolymerized CNFs/diatomite composite in the chitosan matrix. Moreover, the water solubility decreased from 30% for chitosan control film (CH-0) to 21.06% for films containing 30% diatomite and 5% CNFs (CNFs-D30-5). The scanning electron micrographs showed an overall uniform distribution of copolymerized CNFs/diatomite composite in the chitosan matrix with punctual agglomerations.R. FM. would like to express her gratitude to the Department of Economic Development and Infrastructures of the Basque Government (scholarship of young researchers training) for supporting this research financially. E.R. wants to acknowledge the tenure track position "Biobased materials" part of E2S UPPA supported by the "Investissements d'Avenir" French program managed by ANR (ANR16IDEX0002) . The authors would like to acknowledge the technical and human support provided by SGIker (UPV/EHU/ERDF.EU) and Biotechnology Institute, Ankara University, Turkey. Documen

Life Cycle Assessment of various biorefinery approaches for the valorisation of almond shells

In the near future, sustainable and efficient biorefineries would be essential for the production of commodity chemicals and high-added value compounds. Therefore, in this work, six scenarios differing on the delignification steps and cellulose conversion routes were assessed via Life Cycle Assessment methodology in order to study the environmental impacts derived from the conversion of an abundant agricultural residue (almond shells) into high added-value products and select the most suitable one for large-scale valorisation. The assessments were conducted employing experimental results and processing them by SimaPro software. The main conclusion achieved suggested that the enzymatic hydrolysis of the solid from any delignification step entailed the highest environmental impacts and had the highest relative contribution in all the studied impact categories with a maximum of 74%, which was ascribed to Scenario 5. It was also concluded that the organosolv delignification process affected overall more negatively than the alkaline treatment having bigger impacts especially in abiotic depletion (ADP) and photochemical oxidation (POP) categories. Finally, it can be stated that the best route for valorising the almond shell in a biorefinery facility is composed of autohydrolysis (common for every scenario), alkaline delignification, bleaching and acid hydrolysis steps for the obtaining of oligosaccharides, lignin and nanocrystals as products.Authors want to acknowledge the University of the Basque Country UPV/EHU, as well as the Spanish Ministry of Science and Innovation (CTQ2016-78689-R) for supporting financially this research. L.S. and R.F. would like to acknowledge the Departmentof Economic Development and Infrastructures of the Basque Government (scholarship of young researchers training) . A.M. and I.D, would like to thank the University of the Basque Country (Training of Researcher Staff, PIF17/207 and grant reference DOCREC19/47, respectively)

Eco-friendly isolation and characterization of nanochitin from different origins by microwave irradiation: optimization using response surface methodology

[EN] The extraction of nanochitin from marine waste has attracted great industrial interest due to its unique properties, namely biodegradability, biocompatibility and as a functional reinforcing agent. Conventional acid hydrolysis isolation of nanochitin requires high temperatures and acid concentration, time and energy. Herein, for the first time, microwave irradiation method was used as an eco-friendly approach to isolate nanochitin from different sources. The isolation conditions were optimized through an experimental Box-Behnken design using surface response methodology. The data showed optimal conditions of 1 M HCl, 10.00 min and 124.75 W to obtain lobster nanocrystals; 1 M HCl, 14.34 min and 50.21 W to obtain shrimp nanocrystals; and 1 M HCl, 29.08 min and 54.08 W to obtain squid pen nanofibres, reducing time and HCl concentration. The obtained isolation yields where of 85.30, 79.92 and 80.59 % for lobster, shrimp and squid, respectively. The morphology of the nanochitins was dependent of the chitin origin, and the lengths of the nanochitins were of 314.74, 386.12 and > 900 nm for lobster, shrimp and squid pen, respectively. The thermal stability of the ensuing nanochitins was maintained after treatment. The results showed that nanochitin could be obtained by using an eco-friendly approach like microwave irradiation.The authors would like to thank the Basque Government (scholarship of young researchers training and project IT1008-16) for supporting financially this research and their gratitude for technical and human support provided by SGIker (UPV/EHU/ERDF, EU). S.C.M.F. is the recipient of an E2S UPPA Research Partnership Chair (MANTA: Marine Materials) supported by the “Investissements d’Avenir” French program managed by ANR (ANR-16-IDEX-0002), the R ́egion Nouvelle-Aquitaine and the Communaut ́e d’Agglom ́eration du Pays Basque, France

Effect of Deterpenated Origanum majorana L. Essential Oil on the Physicochemical and Biological Properties of Chitosan/β-Chitin Nanofibers Nanocomposite Films

Herein, the effect of three deterpenated fractions from Origanum majorana L. essential oil on the physicochemical, mechanical and biological properties of chitosan/β-chitin nanofibers-based nanocomposite films were investigated. In general, the incorporation of Origanum majorana L. original essential oil or its deterpenated fractions increases the opacity of the nanocomposite films and gives them a yellowish color. The water solubility decreases from 58% for chitosan/β-chitin nanofibers nanocomposite film to around 32% for the nanocomposite films modified with original essential oil or its deterpenated fractions. Regarding the thermal stability, no major changes were observed, and the mechanical properties decreased. Interestingly, data show differences on the biological properties of the materials depending on the incorporated deterpenated fraction of Origanum majorana L. essential oil. The nanocomposite films prepared with the deterpenated fractions with a high concentration of oxygenated terpene derivatives show the best antifungal activity against Aspergillus niger, with fungal growth inhibition of around 85.90%. Nonetheless, the only nanocomposite film that does not present cytotoxicity on the viability of L929 fibroblast cells after 48 and 72 h is the one prepared with the fraction presenting the higher terpenic hydrocarbon content (87.92%). These results suggest that the composition of the deterpenated fraction plays an important role in determining the biological properties of the nanocomposite films.This research was funded by the Basque Country Government (IT 1008-16)

New composite materials based on nanochitin and essential oils

282 p.En los últimos años, el aislamiento de la quitina, que es el segundo polímero natural más abundante después de la celulosa, a partir de residuos de cáscaras de crustáceos ha generado un gran interés para su aplicación en diferentes campos. La quitina es un material de soporte en la naturaleza, y presenta una estructura micro y nanofibrilada altamente organizada por lo que es posible obtener nanoquitina (nanocristales y nanofibras). Éstos presentan excelentes propiedades como baja densidad, biocompatibilidad, baja toxicidad, biodegradabilidad y además mejoran las propiedades mecánicas actuando como refuerzo de los films. Por otro lado, los aceites esenciales son una mezcla compleja de compuestos volátiles extraídos de diferentes partes de las plantas que son una buena fuente de compuestos bioactivos con propiedades antioxidantes y antimicrobianas. Por todo ello, el objetivo de esta tesis fue el desarrollo de nanocomposite films basados en nanoquitina y (bio)polímeros, en particular el quitosano, como matriz y aceites esenciales, como compuestos bioactivos, con el fin de promover la valorización de residuos marinos y reducir la contaminación. Los resultados demostraron que la adición de nanoquitina reforzaba los films y, además, su adición junto con los aceites esenciales mejoró sus propiedades funcionales, incluidas su actividad biológica (antioxidante y antifúngica). Por tanto, podrían emplearse como envases alimentarios inteligentes

Understanding the effects of copolymerized cellulose nanofibers and diatomite nanocomposite on blend chitosan films

Funding Information: R. F-M. would like to express her gratitude to the Department of Economic Development and Infrastructures of the Basque Government (scholarship of young researchers training) for supporting this research financially. E.R. wants to acknowledge the tenure track position “Biobased materials” part of E2S UPPA supported by the “Investissements d'Avenir” French program managed by ANR (ANR-16-IDEX-0002). The authors would like to acknowledge the technical and human support provided by SGIker (UPV/EHU/ERDF.EU) and Biotechnology Institute, Ankara University, Turkey. Funding Information: R. F-M. would like to express her gratitude to the Department of Economic Development and Infrastructures of the Basque Government (scholarship of young researchers training) for supporting this research financially. E.R. wants to acknowledge the tenure track position ?Biobased materials? part of E2S UPPA supported by the ?Investissements d'Avenir? French program managed by ANR (ANR-16-IDEX-0002). The authorswould like to acknowledge the technical and human support provided by SGIker (UPV/EHU/ERDF.EU) and Biotechnology Institute, Ankara University, Turkey. Publisher Copyright: © 2021 The Author(s)Chitosan films lack various important physicochemical properties and need to be supplemented with reinforcing agents to bridge the gap. Herein, we have produced chitosan composite films supplemented with copolymerized (with polyacrylonitrile monomers) cellulose nanofibers and diatomite nanocomposite at different concentrations. The incorporation of CNFs and diatomite enhanced the physicochemical properties of the films. The mechanical characteristics and hydrophobicity of the films were observed to be improved after incorporating the copolymerized CNFs/diatomite composite at different concentrations (CNFs: 1%, 2% and 5%; diatomite: 10% and 30%). The antioxidant activity gradually increased with an increasing concentration (1–5% and 10–30%) of copolymerized CNFs/diatomite composite in the chitosan matrix. Moreover, the water solubility decreased from 30% for chitosan control film (CH-0) to 21.06% for films containing 30% diatomite and 5% CNFs (CNFs-D30-5). The scanning electron micrographs showed an overall uniform distribution of copolymerized CNFs/diatomite composite in the chitosan matrix with punctual agglomerations.Peer reviewe

Contributions of Women in Recent Research on Biopolymer Science

International audienceNowadays, biopolymers are playing a fundamental role in our society because of the environmental issues and concerns associated with synthetic polymers. The aim of this Special Issue entitled ‘Women in Polymer Science and Technology: Biopolymers’ is highlighting the work designed and developed by women on biopolymer science and technology. In this context, this short review aims to provide an introduction to this Special Issue by highlighting some recent contributions of women around the world on the particular topic of biopolymer science and technology during the last 20 years. In the first place, it highlights a selection of important works performed on a number of well-studied natural polymers, namely, agar, chitin, chitosan, cellulose, and collagen. Secondly, it gives an insight into the discovery of new polysaccharides and enzymes that have a role in their synthesis and in their degradation. These contributions will be paving the way for the next generation of female and male scientists on this topic