Preparation and Characterization of Lignin Nanoparticles from Different Plant Sources.

This article presents new research on producing lignin nanoparticles (LNPs) using the antisolvent nanoprecipitation method. Acetone (90%) served as the lignin solvent and water (100%) as the antisolvent, using five types of lignins from various sources. Comprehensive characterization techniques, including NMR, GPC, FTIR, TEM, and DLS, were employed to assess both lignin and LNP properties. The antioxidant activity of the LNPs was evaluated as well. The results demonstrated the successful formation of spherical nanoparticles below 100 nm with initial lignin concentrations of 1 and 2%w/v. The study highlighted the crucial role of lignin purity in LNP formation and colloidal stability, noting that residual carbohydrates adversely affect efficiency. This method offers a straightforward, environmentally friendly approach using cost-effective solvents, applicable to diverse lignin sources. The innovation of this study lies in its demonstration of a cost-effective and eco-friendly method to produce stable, nanometric-sized spherical LNPs. These LNPs have significant potential as reinforcement materials due to their reinforcing capability, hydrophilicity, and UV absorption. This work underscores the importance of starting material purity for optimizing the process and achieving the desired nanometric dimensions, marking a pioneering advancement in lignin-based nanomaterials.

A comprehensive review on processing, characteristics, and applications of cellulose nanofibrils/graphene hybrid-based nanocomposites: Toward a synergy between two-star nanomaterials.

Nanostructured materials are fascinating since they are promising for intensely enhancing materials' performance, and they can offer multifunctional features. Creating such high-performance nanocomposites via effective and mild approaches is an inevitable requirement for sustainable materials engineering. Nanocomposites, which combine two-star nanomaterials, namely, cellulose nanofibrils (CNFs) and graphene derivatives (GNMs), have recently revealed interesting physicochemical properties and excellent performance. Despite numerous studies on the production and application of such systems, there is still a lack of concise information on their practical uses. In this review, recent progress in the production, modification, properties, and emerging uses of CNFs/GNMs hybrid-based nanocomposites in various fields such as flexible energy harvesting and storage, sensors, adsorbents, packaging, and thermal management, among others, are comprehensively examined and described based on recent investigations. Nevertheless, numerous challenges and gaps need to be addressed to successfully introduce such nanomaterials in large-scale industrial applications. This review will certainly help readers understand the design approaches and potential applications of CNFs/GNMs hybrid-based nanocomposites for which new research directions in this emerging topic are discussed.

Thermal and mechanical properties of polyethylene glycol (PEG)-modified lignin/polylactic acid (PLA) biocomposites.

In this study, a method was proposed to prepare biocomposites from polylactic acid (PLA) and polyethylene glycol (PEG)-modified lignin using twin-screw extrusion process. The structure of PEG-modified lignin was studied by Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatographic (GPC) analysis. The effects of different contents of soda lignin and PEG-modified lignin on PLA composites were studied by tensile test, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), dynamic mechanical analysis (DMA) and degradation analysis. The experimental results showed that the addition of PEG-modified lignin enhanced the heat resistance of PLA composite. PLA could be combined with up to 30 % PEG-modified lignin, with no significant reduction in tensile strength properties. Compared with PLA-L30, the tensile stress and elongation at break of PLA-PL30 were increased by 26.4 % and 78.9 %, respectively. This approach provided a new way to produce high-performance lignin based-PLA composites and had certain industrial application value.

Structural characterization of modified coconut husk lignin via steam explosion pretreatment as a renewable phenol substitutes.

The effects of steam explosion (SE) pretreatment on the structural properties of lignin isolated from coconut husk (CH) biomass via soda pulping were investigated in this work. The isolated SE lignin was classified as dilute acid impregnation SE lignin (ASEL), water impregnation SE lignin (WSEL), and 2-naphthol impregnation SE lignin (NSEL). The various types of functional groups isolated from SE lignin were characterized and compared using a variety of complementary analyses: FTIR spectroscopy, NMR spectroscopy, GPC chromatography, HPAEC-PAD chromatography and thermal analyses. It was revealed that ASEL has the highest solid recovery with 55.89 % yield as well as the highest sugars content compared to WSEL (45.66 % yield) and NSEL (49.37 % yield). Besides, all isolated SE lignin contain a significant quantity of non-condensed G-type and S-type units but less amount of H-type units as supported by previous research. The SE lignin produced lignin with higher molecular weight (Mw ASEL: 72725 g mol-1 > Mw WSEL: 13112 g mol-1 > Mw NSEL: 6891 g mol-1) seems to influence the success of the synthesis reaction of phenolic resins. Because of the large variances in the physicochemical properties of SE lignin polymers, their structural properties were increased toward numerous alternative techniques in lignin-based applications.

Microwave-Assisted Synthesis of Pd Nanoparticles into Wood Block (Pd@wood) as Efficient Catalyst for 4-Nitrophenol and Cr(VI) Reduction.

Palladium (Pd) nanoparticle catalysis has attracted increasing attention due to its efficient catalytic activity and its wide application in environmental protection and chemical synthesis. In this work, Pd nanoparticles (about 71 nm) were synthesized in aqueous solution by microwave-assisted thermal synthesis and immobilized in beech wood blocks as Pd@wood catalysts. The wood blocks were first hydrothermally treated with 10% NaOH solution to improve the internal structure and increase their porosity, thereby providing favorable attachment sites for the formed Pd nanoparticles. The stable deposition of Pd nanoparticle clusters on the internal channels of the wood blocks can be clearly observed. In addition, the catalytic performance of the prepared Pd@wood was investigated through two model reactions: the reduction of 4-nitrophenol and Cr(VI). The Pd@wood catalyst showed 95.4 g-1 s-1 M-1 of normalized rate constant knorm and 2.03 min-1 of the TOF, respectively. Furthermore, Pd nanoparticles are integrated into the internal structure of wood blocks by microwave-assisted thermal synthesis, which is an effective method for wood functionalization. It benefits metal nanoparticle catalysis in the synthesis of fine chemicals as well as in industrial wastewater treatment.

Development of Chitosan Green Composites Reinforced with Hemp Fibers: Study of Mechanical and Barrier Properties for Packaging Application.

The use of bioresourced packaging materials is an interesting solution for ecological issues. This work aimed to develop novel chitosan-based packaging materials reinforced with hemp fibers (HF). For this purpose, chitosan (CH) films were filled with 15%, 30%, and 50% (w/w) of two kinds of HF: Untreated fibers cut to 1 mm (UHF) and steam exploded fibers (SEHF). The effect of HF addition and HF treatments on chitosan composites was studied in terms of mechanical properties (tensile strength (TS), elongation at break (EB), and Young's modulus (YM)), barrier properties (water vapor (WVP) and oxygen permeabilities), and thermal properties (glass transition (Tg) and melting temperatures (Tm)). The addition of HF, whether untreated or steam exploded, increased the TS of chitosan composites by 34-65%. WVP was significantly reduced by the addition of HF but no significant change was observed for O2 barrier property, which was in the range between 0.44 and 0.68 cm3·mm/m2·d. Tm of the composite films increased from 133 °C for CH films to 171 °C for films filled with 15% SEHF. However, no significant modification was observed for Tg (105-107 °C). The present study showed that the developed biocomposites had improved properties, mainly the mechanical resistance. Their use in food packaging will help industrials the move toward a sustainable development and circular economy.

Influence of Anatomy, Microstructure, and Composition of Natural Fibers on the Performance of Thermal Insulation Panels.

The growing interest in environmentally friendly materials is leading to a re-evaluation of natural fibers for industrial applications in order to meet sustainability and low-cost objectives, especially for thermal insulation of buildings. This paper deals with the chemical and physical characterization of fibers extracted from seagrass (Posidonia oceanica) and alfa grass (Stipa tenacissima) for a possible substitution of synthetic materials for thermal insulation. Hemp (Cannabis sativa), a fiber broadly used, was also studied for comparison. The parameters characterized include porosity, thermal degradation, elemental composition, skeletal and particle density of the fibers as well as investigation of the thermal conductivity of fiber-based panels. Several technologies were involved in investigating these parameters, including mercury intrusion, thermogravimetric analysis, fluorescence spectroscopy, and fluid pycnometry. The fibers showed a degradation temperature between 316 and 340 °C for Posidonia, between 292 and 326 °C for alfa, and between 300 and 336 °C for hemp fibers. A high porosity allied with a reduced pore size was revealed for Posidonia (77%, 0.54 µm) compared to hemp (75%, 0.61 µm) and alfa (57%, 2.1 µm) raw fibers, leading to lower thermal conductivity values for the nonwoven panels based on Posidonia (0.0356-0.0392 W/m.K) compared to alfa (0.0365-0.0397 W/m.K) and hemp (0.0387-0.0427 W/m.K). Bulk density, operating temperature, and humidity conditions have been shown to be determining factors for the thermal performance of the panels.

Cellulose nanofibrils-graphene hybrids: recent advances in fabrication, properties, and applications.

With the fast-developing social economy and the acceleration of industrialization, seeking effective renewable, sustainable, and environmentally friendly resources that show promising properties is an urgent task and a crucial means to achieve sustainable progress in the face of the growing depletion of non-renewable resources and the deterioration of environmental issues. Cellulose nanofibrils (CNFs) are natural polymeric nanomaterials with excellent biocompatibility, biodegradability, good mechanical features, high strength, low density, high specific surface area, and tunable chemistry. Their combination with other nanomaterials, such as graphene derivatives (GNMs), has been demonstrated to be effective since they produce hybrids with outstanding physicochemical properties, tailorable functionality, and high performance. In this review, recent advances in the preparation, modification, and emerging application of CNFs/GNMs hybrids are described and discussed using the latest studies. First, the concise background of nanocellulose and graphene derivatives is provided, followed by the interfacial interactions between CNFs and GNMs. The different hybrids exhibit great promise in separation, adsorption, optics, flexible electronics, energy storage, thermal management, barrier and packaging, and electromagnetic shielding. The main challenges that inhibit the applicability of these hybrids are finally highlighted, and some perspectives for future research directions are provided.

Steam explosion of Aucoumea klaineana sapwood: Membrane separation of acetylated hemicelluloses.

The fractionation of the aqueous effluent of Aucoumea klaineana Pierre (Okoumé) sapwood steam explosion was examined by a sequential-dilution type membrane diafiltration. The permeate and retentate fractions were characterized by HPLC-SEC, HSQC-NMR, FTIR, UV-visible and HPAE-PAD ion chromatography. Diafiltration with 10 kDa regenerated cellulose membrane has been shown to provide efficient fractionation without fouling. O2 and/or O3 acetylated xylans with a lower proportion of O2 and/or O3 acetylated glucomannans were isolated in the retentate (≈35% w/w and 1.08 w/w% based on initial effluent solid content and on initial dry wood respectively, including 65% w/w in the range 9-22 kDa). The molecular weights of the polysaccharides were significantly higher than those obtained by ethanolic precipitation. The permeate concentrated low molecular mass oligomers (90% w/w < 2.3 kDa, 1.88 w/w% based on initial dry wood) composed of pectic sugars, highly acetylated xylans (DS ≈ 0.9) and relatively high proportion of soluble lignin (≈40% w/w) including Lignin-Carbohydrate Complexes (LCCs).

Lignin containing micro and nano-fibrillated cellulose obtained by steam explosion: Comparative study between different processes.

The isolation of lignin containing micro- and nanofibrillated cellulose (L-MNFC) requires a multistep process. In this study, beech wood was pre-treated by steam explosion (SE), refined or pre-treated by 3 SE and grinded until gel formation. A conventional cooking in an autoclave (SC) was applied in order to get a control sample. The effect of bleaching of a SE pulp was also studied. The chemical composition of the pulps was assessed as well as fiber morphology to compare the effect of the different processes. Quality index and energy consumption during the production process were studied. Results showed that SE can replace SC for the production of pulps with higher lignin content: 8-12% wt. and 3% wt., respectively. Gels contain micro and nanofibrillated cellulose and residual fibers with a dispersion of lignin nanoparticles and some nanocrystals. Optimization of the ultrafine grinding step was required to minimize the energy consumption.

A recent advancement on preparation, characterization and application of nanolignin.

Each year, 50 to 70 million tonnes of lignin are produced worldwide as by-products from pulp industries and biorefineries through numerous processes. Nevertheless, about 98% of lignin is directly burnt to produce steam to generate energy for the pulp mills and only a handful of isolated lignin is used as a raw material for the chemical conversion and for the preparation of various substances as well as modification of lignin into nanomaterials. Thus, thanks to its complex structure, the conversion of lignin to nanolignin, attracting growing attention and generating considerable interest in the scientific community. The objective of this review is to provide a complete understanding and knowledge of the synthesis methods and functionalization of various lignin nanoparticles (LNP). The characterization of LNP such as structural, thermal, molecular weight properties together with macromolecule and quantification assessments are also reviewed. In particular, emerging applications in different areas such as UV barriers, antimicrobials, drug administration, agriculture, anticorrosives, the environment, wood protection, enzymatic immobilization and others were highlighted. In addition, future perspectives and challenges related to the development of LNP are discussed.

Steam Explosion Pretreatment of Lignocellulosic Biomass: A Mini-Review of Theorical and Experimental Approaches.

Steam Explosion (SE) is one of the most efficient and environmentally friendly processes for the pretreatment of lignocellulosic biomass. It is an important tool for the development of the biorefinery concept to mitigate the recalcitrance of biomass. However, the two distinct steps of SE, steam cracking and explosive decompression, leading to the breakdown of the lignocellulosic matrix have generally been studied in empiric ways and clarification are needed. This mini-review provides new insights and recommendations regarding the properties of subcritical water, process modeling and the importance of the depressurization rate.

Cascading Recycling of Wood Waste: A Review.

Wood is an increasingly demanded renewable resource and an important raw material for construction and materials. In addition, new consumption habits are leading to the production of ever greater volumes of waste wood, which constitutes a feedstock that can be mobilized for the cascade production of new materials such as particleboard. However, current legislation and wood waste recycling processes need to be improved in order to maximize the volumes that can be reused and to upgrade the properties of the recycled wood. This review describes wood waste flows and volumes available in Europe, the current French and European legislation, and the innovations under development in this field: innovative automated sorting techniques, physical-chemical processes for cleaning residual glue from the surface of wood particles, cleaning of MDF, and bioremediation processes for cleaning hazardous wood contaminated by heavy metals or creosote.

The 'Shellome' of the Crocus Clam Tridacna crocea Emphasizes Essential Components of Mollusk Shell Biomineralization.

Molluscan shells are among the most fascinating research objects because of their diverse morphologies and textures. The formation of these delicate biomineralized structures is a matrix-mediated process. A question that arises is what are the essential components required to build these exoskeletons. In order to understand the molecular mechanisms of molluscan shell formation, it is crucial to identify organic macromolecules in different shells from diverse taxa. In the case of bivalves, however, taxon sampling in previous shell proteomics studies are focused predominantly on representatives of the class Pteriomorphia such as pearl oysters, edible oysters and mussels. In this study, we have characterized the shell organic matrix from the crocus clam, Tridacna crocea, (Heterodonta) using various biochemical techniques, including SDS-PAGE, FT-IR, monosaccharide analysis, and enzyme-linked lectin assay (ELLA). Furthermore, we have identified a number of shell matrix proteins (SMPs) using a comprehensive proteomics approach combined to RNA-seq. The biochemical studies confirmed the presence of proteins, polysaccharides, and sulfates in the T. crocea shell organic matrix. Proteomics analysis revealed that the majority of the T. crocea SMPs are novel and dissimilar to known SMPs identified from the other bivalve species. Meanwhile, the SMP repertoire of the crocus clam also includes proteins with conserved functional domains such as chitin-binding domain, VWA domain, and protease inhibitor domain. We also identified BMSP (Blue Mussel Shell Protein, originally reported from Mytilus), which is widely distributed among molluscan shell matrix proteins. Tridacna SMPs also include low-complexity regions (LCRs) that are absent in the other molluscan genomes, indicating that these genes may have evolved in specific lineage. These results highlight the diversity of the organic molecules - in particular proteins - that are essential for molluscan shell formation.

Water Extraction of Tannins from Aleppo Pine Bark and Sumac Root for the Production of Green Wood Adhesives.

The extraction of condensed tannins from Aleppo pine bark and sumac roots (Brown Rhus tripartitum) was examined in near industrial conditions, using a water medium in the presence of 2% NaHCO3 and 0.5% NaHSO3 at two different temperatures (70 °C and at 100 °C). The tannins extracts were recovered in high yields (~25% of Aleppo pine and ~30% for sumac) with high phenolic contents (>75%). The tannins were characterized by 13C-NMR and MALDI TOF and showed characteristics of procyanidin/prodelphinidin units. The tannins extracted at 100 °C were composed of smaller flavonoid oligomers (DP < 8) compared to those extracted at a lower temperature (DP > 10). Adhesive resin formulations were prepared using Aleppo or sumac tannins and four different cross linkers (hexamine, glutaraldehyde, furfural, and glyoxal). The resins were studied by TMA in bending and tannins-based formaldehyde-free wood particleboards were produced. The panels displayed internal bond strengths > 0.35 MPa with the four hardeners and all of them passed relevant international standard specifications for interior grade panels. The best results were observed with the tannins extracted at 70 °C with furfural as hardener (IB = 0.81 MPa for Aleppo pine and IB = 0.76 MPa for sumac).

Elaboration of hemicellulose-based films: Impact of the extraction process from spruce wood on the film properties.

In this work, steam explosion (STEX), microwave assisted extraction (MAE) and high voltage electrical discharges (HVED) pretreatments have been evaluated for their impact on the physicochemical characteristics of extracted hemicellulosic polymers and on the resulting hemicellulose-based films. Extraction was carried out on spruce sawdust pre-soaked in water (WPS) or 1 M NaOH solution (SPS). The results have shown that STEX pretreatment gave the highest hemicellulose yields (64 and 66 mg g-1 of dry wood from WPS and SPS respectively) followed by MAE and HVED whilst MAE pretreatment produced the highest molecular mass (Mw~66 kDa of arabinoglucoronoxylans from SPS and 56 kDa for galactoglucomannans from WPS). A relatively high acetylation degree was found for STEX WPS (acetylation degree ≈ 0.35) and a high lignin content for STEX SPS (≈12%). Films have been produced by casting using sorbitol as plasticizer. Low oxygen barrier and light transmittance properties were observed for the films obtained from hemicelluloses extracted from SPS due to their high molecular mass and to intermolecular bonding of hemicelluloses and lignin.

Flame Retardancy of Bio-Based Polyurethanes: Opportunities and Challenges.

Sustainable polymers are emerging fast and have received much more attention in recent years compared to petro-sourced polymers. However, they inherently have low-quality properties, such as poor mechanical properties, and inadequate performance, such as high flammability. In general, two methods have been considered to tackle such drawbacks: (i) reinforcement of sustainable polymers with additives; and (ii) modification of chemical structure by architectural manipulation so as to modify polymers for advanced applications. Development and management of bio-based polyurethanes with flame-retardant properties have been at the core of attention in recent years. Bio-based polyurethanes are currently prepared from renewable, bio-based sources such as vegetable oils. They are used in a wide range of applications including coatings and foams. However, they are highly flammable, and their further development is dependent on their flame retardancy. The aim of the present review is to investigate recent advances in the development of flame-retardant bio-based polyurethanes. Chemical structures of bio-based flame-retardant polyurethanes have been studied and explained from the point of view of flame retardancy. Moreover, various strategies for improving the flame retardancy of bio-based polyurethanes as well as reactive and additive flame-retardant solutions are discussed.

Current advancement on the isolation, characterization and application of lignin.

The most critical issues faced by the world nowadays is to provide the sustainability of consumption for energy and natural resources. Lignin is said to be one of the alternative new discoveries best-suited lignocellulosic biomass due to its low cost, sufficient availability and environmentally safe. The valuable properties exhibited by lignin can give broader applications usage such as in composite materials, wood industries, polymer composite industries, pharmaceutical and corrosion inhibitor industries. Many biomass wastes resources, isolation processes and treatments are undergoing development in order to enhance the producing new lignin-based materials on an industrial scale. Therefore, this review discussed on the current knowledge on the structure and chemistry of isolation of lignin from different sources using various common methods, its characterization, properties and its applications.

Nanocellulose: From Fundamentals to Advanced Applications.

Over the past few years, nanocellulose (NC), cellulose in the form of nanostructures, has been proved to be one of the most prominent green materials of modern times. NC materials have gained growing interests owing to their attractive and excellent characteristics such as abundance, high aspect ratio, better mechanical properties, renewability, and biocompatibility. The abundant hydroxyl functional groups allow a wide range of functionalizations via chemical reactions, leading to developing various materials with tunable features. In this review, recent advances in the preparation, modification, and emerging application of nanocellulose, especially cellulose nanocrystals (CNCs), are described and discussed based on the analysis of the latest investigations (particularly for the reports of the past 3 years). We start with a concise background of cellulose, its structural organization as well as the nomenclature of cellulose nanomaterials for beginners in this field. Then, different experimental procedures for the production of nanocelluloses, their properties, and functionalization approaches were elaborated. Furthermore, a number of recent and emerging uses of nanocellulose in nanocomposites, Pickering emulsifiers, wood adhesives, wastewater treatment, as well as in new evolving biomedical applications are presented. Finally, the challenges and opportunities of NC-based emerging materials are discussed.