Obtaining Cellulose Fibers from Almond Shell by Combining Subcritical Water Extraction and Bleaching with Hydrogen Peroxide.

Almond shell (AS) represents about 33% of the almond fruit, being a cellulose-rich by-product. The use of greener methods for separating cellulose would contribute to better exploitation of this biomass. Subcritical water extraction (SWE) at 160 and 180 °C has been used as a previous treatment to purify cellulose of AS, followed by a bleaching step with hydrogen peroxide (8%) at pH 12. For comparison purposes, bleaching with sodium chlorite of the extraction residues was also studied. The highest extraction temperature promoted the removal of hemicellulose and the subsequent delignification during the bleaching step. After bleaching with hydrogen peroxide, the AS particles had a cellulose content of 71 and 78%, with crystallinity index of 50 and 62%, respectively, for those treated at 160 and 180 °C. The use of sodium chlorite as bleaching agent improved the cellulose purification and crystallinity index. Nevertheless, cellulose obtained by both bleaching treatments could be useful for different applications. Therefore, SWE represents a promising green technique to improve the bleaching sensitivity of lignocellulosic residues, such as AS, allowing for a great reduction in chemicals in the cellulose purification processes.

Stability and Composting Behaviour of PLA-Starch Laminates Containing Active Extracts and Cellulose Fibres from Rice Straw.

The stability and composting behaviour of monolayers and laminates of poly (lactic acid) (PLA) and starch with and without active extracts and cellulose fibres from rice straw (RS) were evaluated. The retrogradation of the starch throughout storage (1, 5, and 10 weeks) gave rise to stiffer and less extensible monolayers with lower water vapour barrier capacity. In contrast, the PLA monolayers, with or without extract, did not show marked changes with storage. However, these changes were more attenuated in the bilayers that gained water vapour and oxygen barrier capacity during storage, maintaining the values of the different properties close to the initial range. The bioactivity of the active films exhibited a slight decrease during storage, so the antioxidant capacity is better preserved in the bilayers. All monolayer and bilayer films were fully composted within 90 days but with different behaviour. The bilayer assembly enhanced the biodegradation of PLA, whose monolayer exhibited a lag period of about 35 days. The active extract reduced the biodegradation rate of both mono- and bilayers but did not limit the material biodegradation within the time established in the Standard. Therefore, PLA-starch laminates, with or without the valorised fractions from RS, can be considered as biodegradable and stable materials for food packaging applications.

Antioxidant starch composite films containing rice straw extract and cellulose fibres.

Antioxidant aqueous rice straw (RS) extract was obtained by a combined ultrasound-reflux heating process and cellulose fibres (CF) were purified by bleaching the extraction residue. Both fractions were incorporated into corn starch to obtain films by melt blending and compression moulding. CF (at 3 % wt.) greatly increased the elastic modulus (by 200 %) and tensile strength at break (by 100 %) while reducing film stretchability. Films with CF exhibited the greatest barrier capacity to water vapour and oxygen. The incorporation of RS extract (at 4, 6 and 8 % wt.) plasticised the film's amorphous phase, but also reinforced the matrix to a certain extent. The active films showed a high degree of UV absorption and DPPH radical scavenging capacity. Mono-dose sunflower oil bags were obtained with films with CF and RS extracts that, to a great extent, prevent oil oxidation in an accelerated oxidative test under UV radiation throughout 50 days.

Using rice straw fractions to develop reinforced, active PLA-starch bilayers for meat preservation.

Bilayers from thermoplastic corn starch (TPS) and PLA were obtained, incorporating or not rice straw (RS) valorised fractions: active extract (es) into PLA and cellulose fibres (cf) into TPS films. The films were obtained by thermoprocessing while the bilayers were obtained by thermocompression of the different monolayers (TPS-PLA, TPScf-PLA, TPS-PLAes and TPScf-PLAes). TPS conferred oxygen barrier capacity to the laminates, which was improved by the cf incorporation. The extract slightly reduced the PLA resistance but improved their oxygen barrier capacity. The tensile and barrier properties of the bilayers revealed changes in the performance of each layer associated with the interlayer compound migration. The TPScf-PLAes bags exhibited noticeable antioxidant capacity when used in meat packaging and reduced microbial counts throughout cold storage. Therefore, these bilayers have considerable potential to extend the shelf-life of meat samples, preserving their quality and safety for longer, while using RS fractions permits its valorisation.

Influence of the cellulose purification process on the properties of aerogels obtained from rice straw.

Cellulose aerogels were obtained from purified rice straw cellulose fibres (CF) by applying different extraction methods: the conventional alkaline treatment (ALK) and alternative aqueous extraction based on the ultrasound combined with reflux heating (USHT) and subcritical water extraction (SWE) (160 and 180 °C). The composition and properties of the CFs were significantly affected by the purification process. The USHT treatment was as efficient as the ALK at eliminating the silica content, but the fibres maintained a notable ratio of hemicellulose (∼16 %). The SWE treatments were not so effective at removing silica (15 %) but greatly promoted the selective extraction of hemicellulose, especially at 180 °C (3 %). The CF compositional differences affected their hydrogel formation capacity and the properties of aerogels. A higher hemicellulose content in the CF led to better-structured hydrogels with better water-holding capacity, while the aerogels exhibited a more cohesive structure with thicker walls, higher porosity (99 %) and water vapour sorption capacity, but lower liquid water retention capacity (0.2 g/g). The residual silica content also interfered with the hydrogel and aerogel formation, giving rise to less structured hydrogels and more fibrous aerogels, with lower porosity (97-98 %).

Subcritical Water Extraction for Valorisation of Almond Skin from Almond Industrial Processing.

Almond skin (AS) is an agro-industrial residue from almond processing that has a high potential for valorisation. In this study, subcritical water extraction (SWE) was applied at two temperatures (160 and 180 °C) to obtain phenolic-rich extracts (water-soluble fraction) and cellulose fibres (insoluble fraction) from AS. The extraction conditions affected the composition and properties of both valorised fractions. The dry extracts obtained at 180 °C were richer in phenolics (161 vs. 101 mg GAE. g-1 defatted almond skin (DAS)), with greater antioxidant potential (1.063 vs. 1.490 mg DAS.mg-1 DPPH) and showed greater antibacterial effect (lower MIC values) against L. innocua (34 vs. 90 mg·mL-1) and E. coli (48 vs. 90 mg·mL-1) than those obtained at 160 °C, despite the lower total solid yield (21 vs. 29%) obtained in the SWE process. The purification of cellulose from the SWE residues, using hydrogen peroxide (H2O2), revealed that AS is not a good source of cellulose material since the bleached fractions showed low yields (20-21%) and low cellulose purity (40-50%), even after four bleaching cycles (1 h) at pH 12 and 8% H2O2. Nevertheless, the application of a green, scalable, and toxic solvent-free SWE process was highly useful for obtaining AS bioactive extracts for different food, cosmetic, or pharmaceutical applications.

Application of Ultrasound Pre-Treatment for Enhancing Extraction of Bioactive Compounds from Rice Straw.

The extraction of water-soluble bioactive compounds using different green methods is an eco-friendly alternative for valorizing agricultural wastes such as rice straw (RS). In this study, aqueous extracts of RS (particles < 500 µm) were obtained using ultrasound (US), reflux heating (HT), stirring (ST) and a combination of US and ST (USST) or HT (USHT). The extraction kinetics was well fitted to a pseudo-second order model. As regards phenolic compound yield, the US method (342 mg gallic acid (GAE). 100 g-1 RS) was more effective than the ST treatment (256 mg GAE.100 g-1 RS), reaching an asymptotic value after 30 min of process. When combined with HT (USHT), the US pre-treatment led to the highest extraction of phenolic compounds from RS (486 mg GAE.100 g-1 RS) while the extract exhibited the greatest antioxidant activity. Furthermore, the USHT extract reduced the initial counts of Listeria innocua by 1.7 logarithmic cycles. Therefore, the thermal aqueous extraction of RS applying the 30 min US pre-treatment, represents a green and efficient approach to obtain bioactive extracts for food applications.