Integral valorisation of walnut shells based on a three-step sequential delignification.

Walnut kernels represent no more than 50-60% of the total weight of the fruit, so the sum of walnut shells generated every year is immense. Nonetheless, these shells could be further valorised for the extraction of their main constituents following a biorefinery scheme. Hence, the objective of this work was an integral valorisation of walnut shells, which involved a sequential organosolv delignification (200 °C, 90 min, 70/30 v/v EtOH/H2O, LSR 6:1) and several posterior non-isothermal hydrothermal treatments (180, 195 and 210 °C, LSR 8:1). Moreover, the spent solids after the aforementioned treatments were evaluated as possible sources of cellulose nanocrystals. The results showed that the sequential organosolv delignifications presented relative lignin yields up to 60%, which leaded to lignins that just differed on their molecular weight distributions. The hydrothermal treatments were efficient for the removal of still present hemicelluloses (14.7-71.8%), and permitted a successful cellulose nanocrystal obtaining whereas the spent solid from the delignification stages did not. Thus, this study presented an innovative strategy for the integral valorisation of walnut shells.

Assessment of Bleached and Unbleached Nanofibers from Pistachio Shells for Nanopaper Making.

Cellulose and lignocellulose nanofibrils were extracted from pistachio shells utilizing environmentally friendly pulping and totally chlorine-free bleaching. The extracted nanofibers were used to elaborate nanopaper, a continuous film made by gravimetric entanglement of the nanofibers and hot-pressed to enhance intramolecular bonding. The elaborated nanopapers were analyzed through their mechanical, optical, and surface properties to evaluate the influence of non-cellulosic macromolecules on the final properties of the nanopaper. Results have shown that the presence of lignin augmented the viscoelastic properties of the nanopapers by ≈25% compared with fully bleached nanopaper; moreover, the hydrophobicity of the lignocellulose nanopaper was achieved, as the surface free energy was diminished from 62.65 to 32.45 mNm-1 with an almost non-polar component and a water contact angle of 93.52°. On the other hand, the presence of lignin had an apparent visual effect on the color of the nanopapers, with a ΔE of 51.33 and a ΔL of -44.91, meaning a substantial darkening of the film. However, in terms of ultraviolet transmittance, the presence of lignin resulted in a practically nonexistent transmission in the UV spectra, with low transmittance in the visible wavelengths. In general, the presence of lignin resulted in the enhancement of selected properties which are desirable for packaging materials, which makes pistachio shell nano-lignocellulose an attractive option for this field.

Lignins from Agroindustrial by-Products as Natural Ingredients for Cosmetics: Chemical Structure and In Vitro Sunscreen and Cytotoxic Activities.

The growing concern about the environmental impact and human health risk related to the excessive use of synthetic ingredients in cosmetics and topical formulations calls for the exploration of safe and sustainable natural alternatives. Lignin-rich lignocellulosic industrial wastes such as hazelnut and walnut shells were used as a lignin polymer source. Agro-derived lignins were evaluated as a potential natural active ingredient for health care products. Aside from the structural characteristics of isolated lignins, which were identified by GPC, Py-GC-MS, and 2D HSQC NMR techniques, functional properties such as antioxidant power and UV absorption ability were investigated. The SPF values found for creams containing 5% of hazelnut and walnut lignin content were 6.9 and 4.5, respectively. Additionally, both lignin types presented appropriate protection against UVA radiation, highly interesting property to block the full ultraviolet spectrum. The biological activity of isolated lignins assessed at different concentrations (0.01-1 mg/mL) and different times (24, 48, and 72 h) on murine fibroblast cell line 3T3 suggested their suitability for cosmetic applications.

Formulation of Multifunctional Materials Based on the Reaction of Glyoxalated Lignins and a Nanoclay/Nanosilicate.

Two organosolv lignins from different origins, namely, almond shells and maritime pine, were modified by using a nanoclay and nanosilicate. Prior to modification, they were activated via glyoxalation to enhance the reactivity of the lignins and thus ease the introduction of the nanoparticles into their structure. The lignins were characterized by several techniques (Fourier transformed infrared, high-performance size exclusion chromatography, 1H NMR, X-ray diffraction, and thermogravimetric analysis) before and after modification to elucidate the main chemical and structural changes. The reaction with glyoxal proved to increase the amount of hydroxyl groups and methylene bridges. This tendency was more pronounced, as the percentage of glyoxal was incremented. On the other side, the addition of the nanoclay and nanosilicate particles improved the thermal stability of the lignins compared to that of the original unmodified ones. This trend was more evident for the lignin derived from maritime pine, which displayed better results regarding the thermal stability, indicating a more effective combination of the nanoparticles in the lignin structure during the modification process.

Lignin depolymerisation strategies: towards valuable chemicals and fuels.

Research on lignin deconstruction has recently become the center of interest for scientists and companies worldwide, racing towards harvesting fossil-fuel like aromatic compounds which are so durably put together by plants as products of millions of years of evolution. The natural complexity and high stability of lignin bonds (also as an evolutionary adaptation by plants) makes lignin depolymerization a highly challenging task. Several efforts have been directed towards a more profound understanding of the structure and composition of lignin in order to devise pathways to break down the biopolymer into useful compounds. The present contribution aims to provide an overview of key advances in the field of lignin depolymerisation. Protocols and technologies will be discussed as well as critically evaluated in terms of possibilities and potential for further industrial implementation.

Exploring chemical reactions to enhance thermal and dispersion stability of kraft and organosolv lignin.

Lignin has been overlooked and used as a waste for long due to its complex and partially hydrophobic structure. Many efforts have been carried out to overcome these deficiencies and apply it as a high-value product, which are insufficient to reach the full potential of lignin in various advanced applications, since they require with procedures for the obtaining of more specific and fine-tuned chemical structures. This work focuses on the obtaining of differently structured hydrophilic lignins derived both from Kraft and organosolv isolation processes. The chemical structures of the different lignin types were studied, and the effect of the structural differences in the modification processes and their subsequent properties analyzed, valorizing their potential application for diverse purposes. The carboxymethylation and sulfomethylation reactions were carried out with the aim of enhancing the polarity of the lignin samples, while the methylation reaction aimed to obtain lignins with higher stability. The physicochemical analyses of the samples, carried out by FTIR, GPC, 31P NMR, 13C NMR, and HSQC NMR, verified the effectiveness of the chemical reactions and conditions selected, obtaining lignins with lower hydroxyl content, due to their substitution and insertion of carboxymetyl, sulfomethyl and methyl groups, therefore obtaining more condensed, aromatic and oxygenated aromatic carbon structures. While the methylation reaction was the most efficient in substituting the OH groups, due to its non-selectivity, OL showed higher modification yields than KL. In terms of the thermal and morphological properties, analyzed by DLS and TGA respectively, it was observed that the modified samples showed lower Z potential values, along with higher conductivity, being the sulfomethylated organosolv lignin the one showing the best results, which was also the one with the smallest particle size and polydispersity index. Finally, all the modified samples showed higher T50% values, suggesting a better stability towards degradation.

Valorisation of crude glycerol in the production of liquefied lignin bio-polyols for polyurethane formulations.

Bio-polyols, produced by liquefying lignin with polyhydric alcohols, offer a promising alternative to conventional polyols for polyurethane production. To enhance the sustainability on the production of these bio-polyols, this study proposes the use of crude glycerol and microwave-assisted liquefaction as substitutes for conventional methods and commercial glycerol. This approach reduces the energy requirements of the reaction while also adding value to this by-product. The synthesis of bio-polyols with suitable properties to produce elastic and rigid polyurethane was carried out using previously optimised reaction conditions. Organosolv lignins obtained from Eucalyptus globulus and Pinus radiata were employed, using polyethylene glycol and crude glycerol as solvents and sulphuric acid as a catalyst. Several parameters of the bio-polyols were analysed, including hydroxyl number (IOH), acid number (An), and functionality (f), suggesting that the bio-polyols were suitable for polyurethane synthesis. Bio-polyols formulated to produce rigid polyurethanes exhibited IOH values of 554 and 383 (mg KOH/g), An values of 1.91 and 4.21 (mg KOH/g), and functionalities of 4.16 and 3.14 for Eucalyptus globulus and Pinus radiata lignin. In the case of bio-polyols for elastic polyurethanes, the values were 228 and 173 (mg KOH/g) (IOH), 20.94 and 25.09 (mg KOH/g) (An), and functionalities of 3.51 and 2.08.

Hydrothermal treatments of walnut shells: A potential pretreatment for subsequent product obtaining.

Walnuts are nowadays widely consumed. Since the edible part of walnuts does not account more than 50-60% of their total weight, the total amount of shells produced annually is huge. However, as walnut shells are part of lignocellulosic biomass, they could be valorised via a biorefinery approach in order to extract their diverse constituents. For this reason, the aim of this work was to valorise walnut shells by a biorefinery scheme. The latest involved multiple microwave assisted and conventional hydrothermal treatments for the subsequent valorisation of oligosaccharides. Then, an organosolv delignification of the solid that permitted the maximum oligosaccharide yield was performed, in order to isolate the lignin. Finally, it was treated for cellulose nanocrystal obtaining. The results showed, on the one hand, that the hydrothermal treatments leaded to xyloligossacharide-rich liquors (1-17 g/L). On the other hand, the organosolv delignification resulted into the extraction of a highly pure lignin (93.6%) and a weight average molecular weight of 7000 Da. Moreover, the solid from the delignification treatment was suitable for a successful nanocrystal production. The extracted fractions could be employed in many applications and could be considered renewable precursors for new materials and chemicals. Hence, the proposed biorefinery scheme would allow an integral valorisation of currently undervalued walnut shells.

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.

Nanofibrillated Cellulose-Based Aerogels Functionalized with Tajuva (Maclura tinctoria) Heartwood Extract.

Aerogels are 3-D nanostructures of non-fluid colloidal interconnected porous networks consisting of loosely packed bonded particles that are expanded throughout their volume by gas and exhibit ultra-low density and high specific surface area. Cellulose-based aerogels can be obtained from hydrogels through a drying process, replacing the solvent (water) with air and keeping the pristine three-dimensional arrangement. In this work, hybrid cellulose-based aerogels were produced and their potential for use as dressings was assessed. Nanofibrilated cellulose (NFC) hydrogels were produced by a co-grinding process in a stone micronizer using a kraft cellulosic pulp and a phenolic extract from Maclura tinctoria (Tajuva) heartwood. NFC-based aerogels were produced by freeze followed by lyophilization, in a way that the Tajuva extract acted as a functionalizing agent. The obtained aerogels showed high porosity (ranging from 97% to 99%) and low density (ranging from 0.025 to 0.040 g·cm-3), as well a typical network and sheet-like structure with 100 to 300 µm pores, which yielded compressive strengths ranging from 60 to 340 kPa. The reached antibacterial and antioxidant activities, percentage of inhibitions and water uptakes suggest that the aerogels can be used as fluid absorbers. Additionally, the immobilization of the Tajuva extract indicates the potential for dentistry applications.

Enhancement of UV absorbance and mechanical properties of chitosan films by the incorporation of solvolytically fractionated lignins.

In this work, an effective sequential organic solvent extraction of kraft and organosolv lignins was carried out to separate lignin into more homogeneous fractions with specific properties. The selected solvents were ethyl acetate, ethanol, methanol, and acetone in that order. Fractions were analysed in terms of their yield, molecular weight, S/G ratio, and phenolic hydroxyl groups content. The incorporation of lignin fractions into the chitosan was aimed to increase the UV absorbance and the mechanical resistance of the chitosan films, which would provide good properties for applications in the packaging field. Films were analysed in terms of UV-vis absorption spectra, tensile strength, as well as colour changes. Results showed a significant increase in the absorbance of UV-A and UV-B with the addition of lignin fractions, mechanical properties showed an increase in the ultimate tensile strength in case of kraft fractions, while organosolv fractions do not affect tensile strength significantly.

Organic acids as a greener alternative for the precipitation of hardwood kraft lignins from the industrial black liquor.

The use of three organic acids such as acetic, lactic and citric acid has been investigated as green precipitation agents for kraft lignin isolation from the industrial hardwood black liquor. Chemical composition, molecular structure characteristics in addition to thermal and antioxidant properties were evaluated and compared to kraft lignin precipitated with sulfuric acid. A clear influence of the organic acids was observed in the chemical composition and molecular properties. Organic acids generated lignins with high purity and low ash and carbohydrate contents. FT-IR and Py-GC-MS analyses revealed the ability of organic acids to produce lignins with greater content of methoxylated structures and carbonyl groups than sulfuric acid. Moreover, all evaluated kraft lignins exhibited a suitable radical scavenging activity, and higher than found for commercial antioxidant used as control. TG analysis showed that the employment of organic acids with higher ionic strength lead less thermally stable kraft lignin. In addition, the proximate analysis confirmed the high potential of kraft lignins as an energy source (21-24 MJ/Kg).

Multiproduct biorefinery based on almond shells: Impact of the delignification stage on the manufacture of valuable products.

In this work, an integral valorisation of almond shells through a biorefinery approach was studied. The three main components of almond shells were extracted, isolated and characterised. The autohydrolysis process permitted the extraction of the hemicellulosic fraction obtaining a liquor rich in xylooligosaccharides (22.12 g/L). Then, two different delignification processes, alkaline and organosolv treatments, were proposed to obtain a very high purity lignin (≈90%) which could be further valorised for a wide variety of applications. The valorisation of the high cellulosic content of the delignified solids was carried out using two different methods. On the one hand, producing cellulose nanocrystals and on the other hand obtaining glucose by an enzymatic hydrolysis as well as a spent solid mainly composed by lignin (≈78 wt%). Thus, the proposed biorefinery approach could contribute to a circular economy as all the main components of the almond shells could be revalorised by environmentally friendly procedures.

Production and characterization of lignin and cellulose fractions obtained from pretreated vine shoots by microwave assisted alkali treatment.

This work deals with the optimization of the second stage of a biorefinery scheme to separate simultaneously cellulose and lignin from hydrothermally pre-treated vine shoots. For this, the suitability of the microwave-assisted alkaline delignification was assessed and optimized through a Box-Wilson experimental design. The optimum conditions (150 °C, 6 wt% NaOH, 30 min) allowed maximizing the lignin removal (82 wt%) and minimizing the loss of the cellulose (35 wt%) present in the pre-treated vine shoots. A thorough characterization of the two fractions obtained at optimum conditions was performed: the cellulose rich solid was analyzed by XRD and FTIR and the lignin was subjected to HPSEC, Py/GC-MS, 13C- and 1H NMR. This purposed second stage would allow performing an integral biorefinery with low energy requirements and environmentally friendly conditions. This approach aligns with the circular economy and the zero waste production philosophies, promoting the sustainable development.

In vitro cytotoxicity studies of industrial Eucalyptus kraft lignins on mouse hepatoma, melanoma and Chinese hamster ovary cells.

Kraft lignin is a polyphenolic compound generated as a by-product from the kraft pulping process in large quantities annually worldwide. In addition to its commercial availability, its structural features make it worth to be considered in the pharmaceutical area. The present study was carried out to evaluate in vitro antioxidant and cytotoxic properties of kraft lignin on mouse hepatoma MH-22A, melanoma B16 (tumor cells) and Chinese hamster ovary (CHO, non-cancerous) cells. Moreover, several analytical techniques were used in order to elucidate the chemical structure of isolated industrial lignins (FT-IR, GPC, Py-GC-MS, 2D HSQC NMR). Results revealed high phenolic content in their composition, high-condensed structure and high phenolic hydroxyls group content. DPPH and ABTS⁎+ radical scavenging assays demonstrated their strong antioxidant activity, which was higher than found for commercial antioxidant (BHT). Kraft lignins act cytotoxically inducing apoptosis- and necrosis-like processes on both on tumor and normal cells. However, the results evidenced that MH-22A cells showed greater sensitive behavior than B16 and non-cancerous CHO cells, which were more tolerant of kraft lignin.

Current advancements in chitosan-based film production for food technology; A review.

Chitosan is obtained from chitin, which could be considered to be the most abundant polymer after cellulose. Owing to these properties, chitosan alone or chitosan-based composite film production is attaining huge attention in terms of applications from researchers and industrialists coming from divergent fields. To enhance the biological (mainly antimicrobial and antioxidant) and physiological (mainly mechanical, thermal and barrier) attributes of the chitosan-based films, a vast medley of plant extracts and supporting polymers has been blended into chitosan films. Considering the up to date literature reports based on chitosan film production and applications, it can be stated that still, the research ratio is low in this field. Chitosan blend/composite films with specific properties (superhydrophobicity, excellent mechanical strength, acceptable barrier properties) can be produced only for specific applications in food technology. In the current review, we tried to summarize the advancements made in the last 5-7 years in the field of chitosan film technology for its application in the food industry.

Production of novel chia-mucilage nanocomposite films with starch nanocrystals; An inclusive biological and physicochemical perspective.

In the current study, chia mucilage composite films with starch nanocrystals (3% and 6%) were produced. The films were analyzed physicochemically (FT-IR, AFM, TGA, DSC), mechanically (Tensile strength and contact angle) and biologically (antimicrobial, antioxidant and cytotoxicity) properties. The incorporation of starch nanocrystals was confirmed through FT-IR spectra showing broad OH peak and CO stretching and shift in NH bending vibrations to the lower wave number. Starch nanocrystals enhanced (control 287.23 °C, film with 3% SNC 286.91 °C and film with 6% mucilage 289.41 °C) the thermal properties of the composite films. The Young Modulus of the film showed an increase after the incorporation of starch nanocrystals due to the strong interaction between mucilage and nanocrystals. On the other hand, the overall hydrophobicity of mucilage composite film decreased due to the hydrophilic nature of cornstarch nanocrystals. MTT assay for cell proliferation revealed significant inhibition of cancer cell (HepG2) lines and exhibits a very low inhibition of epithelial cell line (Vero). Starch nanocrystals enhanced the antibacterial and antioxidant (threefold increase compare to control) properties of mucilage composite films. Mucilage-SNC composite films could be a good therapeutic gain for control and directed drug delivery, food packaging, food coating.

Multistage treatment of almonds waste biomass: Characterization and assessment of the potential applications of raw material and products.

Almond shells are waste biomass generated in agro-industrial activities, which represent a resource that can be further valorized upon treatment. The purpose of this work was to assess new value-added products obtained through a novel multi-stage delignification process of almond shells. A comprehensive chemical characterization of the raw materials and products involved in each stage of the process was carried out. Moreover, an extensive mass balance was developed, providing a full understanding of the extraction process. The pulps produced did not display a significant cellulose loss and hence they could be exploited as cellulose-rich materials. On the other hand, the obtained lignins presented high purity values (≈90%) and a high reactivity, and their structures became more condensed and homogeneous after each extraction cycle. These features would allow their utilization as feedstock of renewable materials such bio-sourced phenolic resins.

Effect of different animal fat and plant oil additives on physicochemical, mechanical, antimicrobial and antioxidant properties of chitosan films.

Practical application of chitosan-essential oil blend films is limited due to the uneconomical extraction procedure of essential oils from plants. This study aimed to produce chitosan films blended with low cost and commercially available oils and fats consumed in daily human diet (olive, corn and sunflower oils, butter and animal fats). The study also focused on how physicochemical, biological and mechanical properties of chitosan blend films were influenced by the incorporation of oils and fats with varying unsaturation degrees. Possible interactions of chitosan film matrix with incorporated oils or fats were investigated. Chitosan-olive oil film showed better surface morphology and higher thermal stability than the films with other unsaturated oils. Tensile strength, Young's modulus and elongation at break were improved by 57.2%, 25.1% and 31.7% for chitosan-olive oil film, respectively. Chitosan-olive oil blend film had the highest antibacterial activity (almost equal to that of commercial antibiotic gentamicin). Edible films obtained from by incorporation of natural oils and fats into chitosan can help produce an environmentally friendly packaging material that is low cost and easily manufactured.

False flax (Camelina sativa) seed oil as suitable ingredient for the enhancement of physicochemical and biological properties of chitosan films.

To overcome the drawbacks of synthetic films in food packaging industry, researchers are turned to natural bio-based edible films enriched with various plant additives. In current study chitosan blend films were produced by incorporating Camelina sativa seed oil at varying concentrations to chitosan matrix. The chitosan blend films were characterized both physicochemically (structural, morphological, thermal, optical and mechanical) and biologically (antimicrobial and antioxidant activity). The incorporation of C. sativa seed oil notably enhanced thermal stability, antioxidative, anti-quorum sensing and antimicrobial activity. Except elongation at break, other mechanical properties of the blend films were not affected by incorporation of C. sativa seed oil. The surface morphology of blend films was recorded as slightly rough, non-porous and fibre-free surface. As it was expected the optical transmittance in visible region was gradually decreased with increasing fraction of seed oil. Interestingly the hydrophilicity of the blend films revealed a swift increase which can be explained by the formation of micelle between glycerol and Tween 40 in blend films. This study provides valuable information for C. sativa seed oil to be used as a blending ingredient in chitosan film technology.