Insecticidal effects of two Tunisian diatomaceous earth loaded with Thymus capitatus (L.) Hoffmans and Links as an ecofriendly approach for stored coleopteran pest control.

This study investigated composition and toxicity of Thyme EOs against two main stored grain insect pests. Carvacrol was distinguished as a major compound (78.34%). In laboratory tests, EOs applied by both direct contact and fumigant tests was more toxic to L. serricorne than T. castaneum. The EOs were also tested combined with two Tunisian Diatomaceous earths (DEs) against T. castaneum. The LC50 was 6.28 µL/L air for natural preparation EO/R1, 5.90 µL/L air for EO/R2 and 121.17 for crude EOs by fumigant test, respectively. While, contact test revealed that natural DEs; dust act as an insecticide with 'LC50' values of 3.22 and 0.29 µL/cm2f or R1 and R2, respectively. Moreover, a significant difference was noted between crude EO, EO/R1 and EO/R2. Overall, the enhancement of the Tunisian DEs' insecticidal activity by its mix with EOs may be a promising active substance as a stored grain protectant.

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.

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.

Optimization of Ultrasound Assisted Extraction of Bioactive Compounds from Apple Pomace.

In the present work, the optimization of the extraction of antioxidant compounds from apple pomace using ultrasound technology as an environmentally friendly and intensification process was developed. Different sonication powers, extraction temperatures and extraction times were studied and their influence on extraction yield and characteristics of the extracted samples (total phenolic compounds, flavonoid content and antioxidant capacity) are presented. The elaborated experimental design and the analysis of Pareto and response surface diagrams allowed us to determine the optimal extraction conditions. The conditions that allow the maximum extraction of phenolic compounds were found at 20 min, 90 °C and 50% ultrasound amplitude. Nevertheless, at these conditions, the antioxidant capacity measured by DPPH decreased in the extracted samples.

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.

Effect of the Chemical Composition of Free-Terpene Hydrocarbons Essential Oils on Antifungal Activity.

In this study, Carum carvi L. essential oil (CEO) and Origanum majorana L. essential oil (MEO) was steam-distillated under reduced pressure. We henceforth obtained three fractions for each essential oil: CF1, CF2, CF3, MF1, MF2, and MF3. Then, these fractions were characterized using the gas chromatography-mass spectrometry (GC-MS) technique. The results indicated that some fractions were rich in oxygenated compounds (i.e., CF2, CF3, MF2, and MF3) with concentrations ranging from 79.21% to 98.56%. Therefore, the influence of the chemical composition of the essential oils on their antifungal activity was studied. For this purpose, three food spoilage fungi were isolated, identified, and inoculated in vitro, in order to measure the antifungal activity of CEO, MEO, and their fractions. The results showed that stronger fungi growth inhibitions (FGI) (above 95%) were found in fractions with higher percentages of oxygenated compounds, especially with (-)-carvone and terpin-4-ol as the major components. Firstly, this work reveals that the free-terpenes hydrocarbons fractions obtained from MEO present higher antifungal activity than the raw essential oil against two families of fungi. Then, it suggests that the isolation of (-)-carvone (97.15 ± 5.97%) from CEO via vacuum distillation can be employed successfully to improve antifungal activity by killing fungi (FGI = 100%). This study highlights that separation under reduced pressure is a simple green method to obtain fractions or to isolate compounds with higher biological activity useful for pharmaceutical products or natural additives in formulations.

Chitin Nanoforms Provide Mechanical and Topological Cues to Support Growth of Human Adipose Stem Cells in Chitosan Matrices.

The precise role and value of incorporating nanoforms in biologically active matrices for medical applications is not known. In our current work, we incorporate two chitin nanoforms (i.e., nanocrystals or nanofibers) into Genipin-chitosan crosslinked matrices. These materials were studied as 2D films and 3D porous scaffolds to assess their potential as primary support and guidance for stem cells in tissue engineering and regenerative medicine applications. The incorporation of either nanoforms in these 2D and 3D materials reveals significantly better swelling properties and robust mechanical performance in contrast to nanoform-free chitosan matrices. Furthermore, our data shows that these materials, in particular, incorporation of low concentration chitin nanoforms provide specific topological cues to guide the survival, adhesion, and proliferation of human adipose-derived stem cells. These findings demonstrate the potential of Genipin-chitosan crosslinked matrices impregnated with chitin nanoforms as value added materials for stem cell-based biomedical applications.

Nectandra grandiflora By-Products Obtained by Alternative Extraction Methods as a Source of Phytochemicals with Antioxidant and Antifungal Properties.

Nectandra grandiflora Nees (Lauraceae) is a Brazilian native tree recognized by its durable wood and the antioxidant compounds of its leaves. Taking into account that the forest industry offers the opportunity to recover active compounds from its residues and by-products, this study identifies and underlines the potential of natural products from Nectandra grandiflora that can add value to the forest exploitation. This study shows the effect of three different extraction methods: conventional (CE), ultrasound-assisted (UAE) and microwave-assisted (MAE) on Nectandra grandiflora leaf extracts (NGLE) chemical yields, phenolic and flavonoid composition, physical characteristics as well as antioxidant and antifungal properties. Results indicate that CE achieves the highest extraction phytochemical yield (22.16%), but with similar chemical composition to that obtained by UAE and MAE. Moreover, CE also provided a superior thermal stability of NGLE. The phenolic composition of NGLE was confirmed firstly, by colorimetric assays and infrared spectra and then by chromatographic analysis, in which quercetin-3-O-rhamnoside was detected as the major compound (57.75-65.14%). Furthermore, the antioxidant capacity of the NGLE was not altered by the extraction methods, finding a high radical inhibition in all NGLE (>80% at 2 mg/mL). Regarding the antifungal activity, there was observed that NGLE possess effective bioactive compounds, which inhibit the Aspergillus niger growth.

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.

The emergence of nanocellulose aerogels in CO2 adsorption.

Mitigating the effect of climate change toward a sustainable development is one of the main challenges of our century. The emission of greenhouse gases, especially carbon dioxide (CO2), is a leading cause of the global warming crisis. To address this issue, various sustainable strategies have been formulated for CO2 capture. Renewable nanocellulose aerogels have risen as a highly attractive candidate for CO2 capture thanks to their porous and surface-tunable nature. Nanocellulose offer distinctive characteristics, including significant aspect ratios, exceptional biodegradability, lightweight nature, and the ability for chemical modification due to the abundant presence of hydroxyl groups. In this review, recent research studies on nanocellulose-based aerogels designed for CO2 absorption have been highlighted. The state-of-the-art of nanocellulose-based aerogel has been thoroughly assessed, including their synthesis, drying methods, and characterization techniques. Additionally, discussions were held about the mechanisms of CO2 adsorption, the effects of the porous structure, surface functionalization, and experimental parameters. Ultimately, this synthesis review provides an overview of the achieved adsorption rates using nanocellulose-based aerogels and outlines potential improvements that could lead to optimal adsorption rates. Overall, this research holds significant promise for tackling the challenges of climate change and contributing to a more sustainable future.

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.

Integral Valorization of Posidonia oceanica Balls: An Abundant and Potential Biomass.

Posidonia oceanica balls (POB), a kind of seagrass, are a significant environmental issue since they are annually discharged onto beaches. Their current usefulness limits interest in their management and enhances the environmental problem. Therefore, in this research, the potential of this lignocellulosic biomass was studied from a holistic biorefinery point of view. To this end, an in-depth study was carried out to select the best pathway for the integral valorization of POBs. First, an autohydrolysis process was studied for the recovery of oligosaccharides. Then, a delignification stage was applied, where, in addition to studying different delignification methods, the influence of the autohydrolysis pre-treatment was also investigated. Finally, cellulose nanofibers (CNFs) were obtained through a chemo-mechanical treatment. The results showed that autohydrolysis not only improved the delignification process and its products, but also allowed the hemicelluloses to be valorized. Acetoformosolv delignification proved to be the most successful in terms of lignin and cellulose properties. However, alkaline delignification was able to extract the highest amount of lignin with low purity. CNFs were also successfully produced from bleached solids. Therefore, the potential of POB as a feedstock for a biorefinery was confirmed, and the pathway should be chosen according to the requirements of the desired end products.

Preparation of Filter Paper from Bamboo and Investigating the Effect of Additives.

As air pollution escalates, the need for air filters increases. It is better that the filters used be based on natural fibers, such as non-wood fibers, which cause low damage to the environment. However, the short fiber lengths, low apparent densities, and high volumes of non-wood materials can make it challenging to prepare filter paper with the required mechanical and physical properties. In that context, this study focused on utilizing bamboo fibers to fabricate filter paper by employing the anthraquinone soda pulping method. The pulp underwent bleaching and oxidation processes, with the incorporation of cationic starch (CS) and polyvinyl alcohol (PVA) to enhance resistance properties, resulting in the creation of handmade filter papers. The findings revealed that the tear, burst, and tensile strength of filter paper increased with the oxidation and addition of CS and PVA. Air permeability increased with addition of PVA and combination of CS and PVA. FTIR demonstrated the conversion of hydroxyl groups in cellulose chains to carboxyl groups due to oxidation. SEM images illustrated alterations in the fiber structure post-oxidation treatment, with CS reducing pores while PVA and the CS-PVA combination enlarged pore size and enhanced porosity. The BET surface area surface area expanded with oxidation and the addition of the CS-PVA blend, indicating heightened filter paper porosity. Notably, the combined inclusion of CS and PVA not only augmented mechanical strength but also increased porosity while maintaining pore size.

Comparison of amino acid release between enzymatic hydrolysis and acid autolysis of rainbow trout viscera.

Fish protein hydrolysates were obtained from cultured rainbow trout (Oncorhynchus mykiss) viscera using commercial and endogenous enzymes. Two methods were employed for hydrolysis: acid autolysis (also known as silage) at room temperature for 10 days in acidic conditions, until total solubilisation, and enzymatic hydrolysis using Alcalase 2.4 LFG, Protana Prime, and the endogenous enzymes in the viscera. The effectiveness of both methods in releasing free amino acids (FAA) was assessed. After evaluating the results, the most effective enzymatic hydrolysis was optimized. The findings indicated that enzymatic hydrolysis with Alcalase, Protana Prime and endogenous enzymes combined for 7 h at a dose of 1% of protein, and a 7-day acid autolysis yielded the highest degree of hydrolysis (83.8% and 75.8%), a yield of FAA from viscera of 5.9% and 3.2%, and a yield of FAA from total protein of 71.3% and 52.5%, respectively. In conclusion, the use of commercial enzymes was more efficient in releasing amino acids, but endogenous enzymes showed a strong proteolytic capacity during acid autolysis, suggesting it also as a promising method to produce FAA-rich hydrolysates.

Elaboration of Thermally Performing Polyurethane Foams, Based on Biopolyols, with Thermal Insulating Applications.

In this work, biobased rigid polyurethane foams (PUFs) were developed with the aim of achieving thermal and fireproofing properties that can compete with those of the commercially available products. First, the synthesis of a biopolyol from a wood residue by means of a scaled-up process with suitable yield and reaction conditions was carried out. This biopolyol was able to substitute completely the synthetic polyols that are typically employed within a polyurethane formulation. Different formulations were developed to assess the effect of two flame retardants, namely, polyhedral oligomeric silsesquioxane (POSS) and amino polyphosphate (APP), in terms of their thermal properties and degradation and their fireproofing mechanism. The structure and the thermal degradation of the different formulations was evaluated via Fourier Transformed Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Likewise, the performance of the different PUF formulations was studied and compared to that of an industrial PUF. From these results, it can be highlighted that the addition of the flame retardants into the formulation showed an improvement in the results of the UL-94 vertical burning test and the LOI. Moreover, the fireproofing performance of the biobased formulations was comparable to that of the industrial one. In addition to that, it can be remarked that the biobased formulations displayed an excellent performance as thermal insulators (0.02371-0.02149 W·m-1·K-1), which was even slightly higher than that of the industrial one.

Gelatin-Based Hydrogels: Potential Biomaterials for Remediation.

Hydrogels have become one of the potential polymers used with great performance for many issues and can be promoted as biomaterials with highly innovative characteristics and different uses. Gelatin is obtained from collagen, a co-product of the meat industry. Thus, converting wastes such as cartilage, bones, and skins into gelatin would give them added value. Furthermore, biodegradability, non-toxicity, and easy cross-linking with other substances can promote polymers with high performance and low cost for many applications, turning them into sustainable products with high acceptance in society. Gelatin-based hydrogels have been shown to be useful for different applications with important and innovative characteristics. For instance, these hydrogels have been used for biomedical applications such as bone reconstruction or drug delivery. Furthermore, they have also shown substantial performance and important characteristics for remediation for removing pollutants from water, watercourse, and effluents. After its uses, gelatin-based hydrogels can easily biodegrade and, thus, can be sustainably used in the environment. In this study, gelatin was shown to be a potential polymer for hydrogel synthesis with highly renewable and sustainable characteristics and multiple uses.

Nanocellulose-based sensors in medical/clinical applications: The state-of-the-art review.

In recent years, the considerable importance of healthcare and the indispensable appeal of curative issues, particularly the diagnosis of diseases, have propelled the invention of sensing platforms. With the development of nanotechnology, the integration of nanomaterials in such platforms has been much focused on, boosting their functionality in many fields. In this direction, there has been rapid growth in the utilisation of nanocellulose in sensors with medical applications. Indeed, this natural nanomaterial benefits from striking features, such as biocompatibility, cytocompatibility and low toxicity, as well as unprecedented physical and chemical properties. In this review, different classifications of nanocellulose-based sensors (biosensors, chemical and physical sensors), alongside some subcategories manufactured for health monitoring, stand out. Moreover, the types of nanocellulose and their roles in such sensors are discussed.

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.