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A novel strategy for pre-treated biomass detoxification combining emerging green solvents and low environmental impact extraction technologies was evaluated. Steam-exploded biomass was subjected to microwave-assisted or orbital shaking extraction using bio-based or eutectic solvents. The extracted biomass was enzymatically hydrolysed. The potential of this detoxification methodology was studied in terms of phenolic inhibitors extraction and sugar production improvement. The effect of adding a post-extraction water washing step before hydrolysis was also evaluated. Excellent results were achieved when steam-exploded biomass was subjected to the microwave-assisted extraction combined with the washing step. The highest sugar production was achieved when ethyl lactate was used as extraction agent (49.80 ± 3.10 g total sugar/L) over the control (30.43 ± 0.34 g total sugar/L). Results suggested that a detoxification step based on green solvents would be a promising option to extract phenolic inhibitors, which can be revalorized as antioxidants, and improve the sugar production from the extracted pre-treated biomass.

Kraft lignin, a side-stream from the pulp and paper industry, can be modified by laccases for the synthesis of high added-value products. This work aims to study different laccase sources, including a bacterial laccase from Streptomyces ipomoeae (SiLA) and a fungal laccase from Myceliophthora thermophila (MtL), for kraft lignin polymerization. To study the influence of some variables in these processes, a central composite design (CCD) with two continuous variables (enzyme concentration and reaction time) and three levels for each variable was used. The prediction of the behavior of the output variables (phenolic content and molecular weight of lignins) were modelled by means of response surface methodology (RSM). Moreover, characterization of lignins was performed by Fourier-transform infrared (FTIR) spectroscopy and different nuclear magnetic resonance (NMR) spectroscopy techniques. In addition, antioxidant activity was also analyzed. Results showed that lignin polymerization (referring to polymerization as lower phenolic content and higher molecular weight) occurred by the action of both laccases. The enzyme concentration was the most influential variable in the lignin polymerization reaction within the range studied for SiLA laccase, while the most influential variable for MtL laccase was the reaction time. FTIR and NMR characterization analysis corroborated lignin polymerization results obtained from the RSM.

During lignocellulosic bioethanol production, the whole slurry obtained by steam explosion is filtered, generating a water-insoluble fraction rich in cellulose which is used for saccharification and ethanol fermentation, as well as a liquid fraction containing solubilised glucose and xylose but also some inhibitory by-products (furan derivatives, weak acids and phenols), which limits its use for this purpose. Since utilization of this liquid fraction to ethanol is essential for an economically feasible cellulosic ethanol process, this work studied a laccase from Myceliophthora thermophila to detoxify the liquid fraction obtained from steam-pretreated olive tree pruning (OTP) and to overcome the effects of these inhibitors. Then, the fermentation of laccase-treated liquid fraction was evaluated on ethanol production by different Saccharomyces cerevisiae strains, including the Ethanol Red, with the capacity to ferment glucose but not xylose, and the xylose-fermenting recombinant strain F12. Laccase treatment reduced total phenols content by 87% from OTP liquid fraction, not affecting furan derivatives and weak acids concentration. Consequently, the fermentative behavior of both Ethanol Red and F12 strains was improved, and ethanol production and yields were increased. Moreover, F12 strain was capable of utilizing some xylose, which increased ethanol production (10.1 g/L) compared to Ethanol Red strain (8.6 g/L).

This work focuses on the structural features and physicochemical properties of different Kraft lignins and how they can influence the electrospinning process to obtain nanostructures. Structural features of Kraft lignins were characterized by nuclear magnetic resonance, size exclusion chromatography, fourier-transform infrared spectroscopy, and thermal analysis, whereas chemical composition was analyzed by standard method. The addition of cellulose acetate (CA) improves the electrospinning process of Kraft lignins (KL). Thus, solutions of KL/CA at 30 wt% with a KL:CA weight ratio of 70:30 were prepared and then physicochemical and rheologically characterized. The morphology of electrospun nanostructures depends on the intrinsic properties of the solutions and the chemical structure and composition of Kraft lignins. Then, surface tension, electrical conductivity and viscosity of eucalypt/CA and poplar/CA solutions were suitable to obtain electrospun nanostructures based on uniform cross-linked nanofibers with a few beaded fibers. It could be related with the higher purity and higher linear structure, phenolic content and S/G ratios of lignin samples. However, the higher values of electrical conductivity and viscosity of OTP/CA solutions resulted in electrospun nanostructure with micro-sized particles connected by thin fibers, due to a lower purity, S/G ratio and phenolic content and higher branched structure in OTP lignin.

Oil-in-water bitumen emulsions stabilized by biobased surfactants such as lignin are in line with the current sustainable approaches of the asphalt industry involving bitumen emulsions for reduced temperature asphalt technologies. With this aim, three lignins, derived from the kraft pulping and bioethanol industries, were chemically modified via the Mannich reaction to be used as cationic emulsifiers. A comprehensive chemical characterization was conducted on raw lignin-rich products, showing that the kraft sample presents a higher lignin concentration and lower molecular weight. Instead, bioethanol-derived samples, with characteristics of non-woody lignins, present a high concentration of carbohydrate residues and ashes. Lignin amination was performed at pH = 10 and 13, using tetraethylene pentamine and formaldehyde as reagents at three different stoichiometric molar ratios. The emulsification ability of such cationic surfactants was firstly studied on prototype silicone oil-in-water emulsions, attending to their droplet size distribution and viscous behavior. Among the synthetized surfactants, cationic kraft lignin has shown the best emulsification performance, being used for the development of bitumen emulsions. In this regard, cationic kraft lignin has successfully stabilized oil-in-water emulsions containing 60% bitumen using small surfactant concentrations, between 0.25 and 0.75%, which was obtained at pH = 13 and reagent molar ratios between 1/7/7 and 1/28/28 (lignin/tetraethylene pentamine/formaldehyde).

The development of nanocellulose-clay materials resulted of great relevance, as it opened up the applications of nanocellulose, but it still requires new approaches that could contribute to improve the preparation procedures and the features of this type of biohybrid materials. In this context, nanocellulose-sepiolite (NC-S) biocomposite foams and films have already been successfully tested for some applications. However, the influence of the nanocellulose properties on sepiolite-cellulose interactions, and consequently on the final properties and potential applications of NC-S biohybrid materials, has not been previously studied. To address this knowledge gap, four kinds of nanocelluloses produced from elm biomass (non-chemically pretreated lignocellulose and bleached cellulose nanofibers (LCNFs and CNFs, respectively), TEMPO-oxidized cellulose nanofibers (TOCNFs) and cellulose nanocrystals (CNCs)) were characterized and used to develop NC-S nanopapers. A stronger interaction was found between sepiolite and negatively charged nanocelluloses (TOCNFs and CNCs), improving their thermal stability and mechanical properties by increasing the sepiolite content. Furthermore, the type of nanocellulose and the sepiolite content could be adjusted to tune the flammability, water permeability and mechanical and optical properties of the NC-S nanopapers. Graphical abstract: [Figure not available: see fulltext.]

In order to identify new sustainable sources for producing cellulose nanofibers (CNFs), fast-growing poplar (Populus alba L.) wood was evaluated herein. For that purpose, bleached poplar kraft pulp was produced and submitted to TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) mediated oxidation (TEMPO-ox) chemical pretreatment followed by microfluidization. The resulting CNFs were thoroughly characterized, including a rheological study at different pH values. Poplar CNFs showed properties comparable to eucalypt CNFs (reference material for CNFs production), showing high carboxylate content (1048 ± 128 µmol g−1), fibrillation yield (87.3% ± 8.1%), optical transmittance (83% at 700 nm) and thermal stability (up to more than 200 °C). Regarding the rheological study, whereas pH from 4 to 10 did not produce significant changes in rheological behavior, a reduction of pH down to 1 led to an order-of-magnitude increase on the viscoelastic functions. Therefore, poplar CNF shows potential in the pH-sensitive hydrogels application field. Finally, the possible ecotoxicity of poplar CNF was assessed. The decrease in cell viability was very low so that only concentrations causing a 10% cytotoxicity could be calculated for the assay detecting alterations in cell metabolism (10 µg mL−1) and plasma membrane integrity (60 µg mL−1).

Cellulose is the most abundant component of biomass and the one that requires the most activation energy (Ea) for pyrolysis. In this study, the dependence of Ea on the intrinsic cellulose characteristics, such as the degree of polymerization (DP), crystallinity, and crystal size, was studied in different cellulose samples, including samples from Eucalyptus globulus, Ulmus minor, Linun usitatissimum, Olea europaea, Robinia pseudoacacia, and Populus alba. Then, to describe the pyrolytic degradation of cellulose, the Ozawa-Flynn-Wall kinetic method was the most appropriate among the isoconversional models studied. An acceptable quadratic relationship of R-2 > 0.9 between the Ea values of the different cellulose samples with their corresponding DP, crystallinity index, and crystal size values was found. Therefore, low crystallinity and low-to-medium crystal size values are desired to obtain lower Ea values for cellulose pyrolysis. On the other hand, DP did not present a clear effect on Ea in the studied DP range. Keywords

Motivated by the negative impact of fossil fuel consumption on the environment, the need arises to produce materials and energy from renewable sources. Cellulose, the main biopolymer on Earth, plays a key role in this context, serving as a platform for the development of biofuels, chemicals and novel materials. Among the latter, micro-and nanocellulose have been receiving increasing attention in the last few years. Their many attractive properties, i.e., thermal stability, high mechanical resistance, barrier properties, lightweight, optical transparency and ease of chemical modification, allow their use in a wide range of applications, such as Paper or polymer reinforcement, Packag-ing, construction, membranes, bioplastics, bioengineering, optics and electronics. In view of the increasing demand for traditional wood pulp (e.g., obtained from eucalypt, birch, pine, spruce) for micro/nanocellulose production, dedicated crops and agricultural residues can be interesting as raw materials for this purpose. This work aims at achieving microfibrillated cellulose production from fast-growing poplar and olive tree pruning using physical pretreatment (PFI refining) before the microfibrillation stage. Both raw materials yielded microfibrillated cellulose with similar properties to that obtained from a commercial industrial eucalypt pulp, producing films with high mechanical properties and low wettability. According to these properties, different applications for cellulose microfibers suspensions and films are discussed.

A prospective methodology aimed to develop totally sustainable oleogels with potential application in lubrication is reported. Oleogels were prepared with cellulose nanofibrils from elm pulps in castor oil. Even at a concentration as low as 1.4 wt%, the oleogels showed rheological behaviors similar to a traditional lithium grease used as reference. In that sense, the high thickening power of cellulose nanofibers was remarked. Never-dried bleached and unbleached elm pulps were mechanically treated with PFI mill refiner and microfluidizer. Moreover, as an alternative way of producing cellulose nanofibrils, the never-dried bleached elm pulp was chemically oxidized using 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO). The three types of nanofibers were characterized and used in the production of oleogels. The great challenge was to remove the high amount of water retained by the nanofibrils during the nanofibrillation treatment before it was incorporated into the vegetable oil-based lubricant. Alternative strategies such as liophilization or drying failed because the nanofibers, with very high specific surface and strong capacity to interact among them by hydrogen bonding, underwent severe aggregation. Instead, the proposed methanol-based solvent exchange method enabled the transfer of the cellulose nanofibrils from the origin hydrogel to the vegetable oil with no detriment of both their aspect ratio and thickening capacity. Chemical considerations are provided with regard to such a solvent-mediated method, which yielded homogeneous and storage-stable oleogels. This work may attract the interest of lubricant manufacturers to produce nanocellulose-based eco-lubricating greases for industrial applications.