The Impact of Lignin Biopolymer Sources, Isolation, and Size Reduction from the Macro- to Nanoscale on the Performances of Next-Generation Sunscreen.

In recent years, concerns about the harmful effects of synthetic UV filters on the environment have highlighted the need for natural sun blockers. Lignin, the most abundant aromatic renewable biopolymer on Earth, is a promising candidate for next-generation sunscreen due to its inherent UV absorbance and its green, biodegradable, and biocompatible properties. Lignin's limitations, such as its dark color and poor dispersity, can be overcome by reducing particle size to the nanoscale, enhancing UV protection and formulation. In this study, 100-200 nm lignin nanoparticles (LNPs) were prepared from various biomass by-products (hardwood, softwood, and herbaceous material) using an eco-friendly anti-solvent precipitation method. Pure lignin macroparticles (LMPs) were extracted from beech, spruce, and wheat straw using an ethanol-organosolv treatment and compared with sulfur-rich kraft lignin (KL). Sunscreen lotions made from these LMPs and LNPs at various concentrations demonstrated novel UV-shielding properties based on biomass source and particle size. The results showed that transitioning from the macro- to nanoscale increased the sun protection factor (SPF) by at least 2.5 times, with the best results improving the SPF from 7.5 to 42 for wheat straw LMPs and LNPs at 5 wt%. This study underscores lignin's potential in developing high-quality green sunscreens, aligning with green chemistry principles.

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.

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.

Functional genomics gives new insights into the ectomycorrhizal degradation of chitin.

Ectomycorrhizal (EcM) fungi play a crucial role in the mineral nitrogen (N) nutrition of their host trees. While it has been proposed that several EcM species also mobilize organic N, studies reporting the EcM ability to degrade N-containing polymers, such as chitin, remain scarce. Here, we assessed the capacity of a representative collection of 16 EcM species to acquire 15 N from 15 N-chitin. In addition, we combined genomics and transcriptomics to identify pathways involved in exogenous chitin degradation between these fungal strains. Boletus edulis, Imleria badia, Suillus luteus, and Hebeloma cylindrosporum efficiently mobilized N from exogenous chitin. EcM genomes primarily contained genes encoding for the direct hydrolysis of chitin. Further, we found a significant relationship between the capacity of EcM fungi to assimilate organic N from chitin and their genomic and transcriptomic potentials for chitin degradation. These findings demonstrate that certain EcM fungal species depolymerize chitin using hydrolytic mechanisms and that endochitinases, but not exochitinases, represent the enzymatic bottleneck of chitin degradation. Finally, this study shows that the degradation of exogenous chitin by EcM fungi might be a key functional trait of nutrient cycling in forests dominated by EcM fungi.

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).

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.

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.

Sapwood and heartwood affect differentially bacterial and fungal community structure and successional dynamics during Quercus petraea decomposition.

In forests, bacteria and fungi are key players in wood degradation. Still, studies focusing on bacterial and fungal successions during the decomposition process depending on the wood types (i.e. sapwood and heartwood) remain scarce. This study aimed to understand the effect of wood type on the dynamics of microbial ecological guilds in wood decomposition. Using Illumina metabarcoding, bacterial and fungal communities were monitored every 3 months for 3 years from Quercus petraea wood discs placed on forest soil. Wood density and microbial enzymes involved in biopolymer degradation were measured. We observed rapid changes in the bacterial and fungal communities and microbial ecological guilds associated with wood decomposition throughout the experiment. Bacterial and fungal succession dynamics were very contrasted between sapwood and heartwood. The initial microbial communities were quickly replaced by new bacterial and fungal assemblages in the sapwood. Conversely, some initial functional guilds (i.e. endophytes and yeasts) persisted all along the experiment in heartwood and finally became dominant, possibly limiting the development of saprotrophic fungi. Our data also suggested a significant role of bacteria in nitrogen cycle during wood decomposition.

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.

High voltage electric discharges treatment for high molecular weight hemicelluloses extraction from spruce.

The aim of this work is to extract hemicelluloses polymers from spruce sawdust using High Voltage Electrical Discharges (HVED) pretreatment. HVED pretreatment was carried out in order to improve deconstruction of the wood matrix and to allow easier release of high molecular mass hemicelluloses. The results revealed the advantage of HVED activation step in the process of extraction. The yield of hemicellulose extraction increased with HVED treatment time. In fact, after 4 ms of HVED treatment time in 1 M NaOH solution, the yield obtained was higher as compared to the untreated sample (19 mg/g of dry matter and 15.8 mg/g of dry matter respectively). The molecular weights of extracted hemicelluloses are very high (55 kDa and 47 kDa for 4 ms of HVED-treatment in 1 M NaOH solution and water respectively). The use of different mediums of extraction with HVED pretreatment have revealed a selective solubilization of spruce hemicelluloses.

Homolytic and Heterolytic Cleavage of ß-Ether Linkages in Hardwood Lignin by Steam Explosion.

Steam-explosion lignin (SEL) was extracted with ethanol from steam-exploded hardwood (okoumé, Aucoumea klaineana Pierre) pretreated at various severities after neutral or acidic impregnation. The SELs were subjected to structural characterization by 2D HSQC NMR, 31P NMR, and SEC and compared with milled-wood lignin (MWL). A strong decrease in the ß- O-4 content is observed with increasing steam-explosion severity accompanied by a gradual increase in molecular mass. Cα-oxidized S units (S', Hibbert's ketones) were quantified by NMR and used as a marker of the hydrolytic mechanism; naphthol was used as a carbonium-ion scavenger. It has been observed that mixed reactions of hydrolysis and homolysis are involved, but the SEL is mainly cleaved homolytically, favoring recondensation through radical coupling even at low reaction severity. However, acidic preimpregnation of wood prior to steam explosion enhanced the carbonium-ion pathway.

Biochemical characterization of the skeletal matrix of the massive coral, Porites australiensis - The saccharide moieties and their localization.

To construct calcium carbonate skeletons of sophisticated architecture, scleractinian corals secrete an extracellular skeletal organic matrix (SOM) from aboral ectodermal cells. The SOM, which is composed of proteins, saccharides, and lipids, performs functions critical for skeleton formation. Even though polysaccharides constitute the major component of the SOM, its contribution to coral skeleton formation is poorly understood. To this end, we analyzed the SOM of the massive colonial coral, Porites australiensis, the skeleton of which has drawn great research interest because it records environmental conditions throughout the life of the colony. The coral skeleton was extensively cleaned, decalcified with acetic acid, and organic fractions were separated based on solubility. These fractions were analyzed using various techniques, including SDS-PAGE, FT-IR, in vitro crystallization, CHNS analysis, chromatography analysis of monosaccharide and enzyme-linked lectin assay (ELLA). We confirmed the acidic nature of SOM and the presence of sulphate, which is thought to initiate CaCO3 crystallization. In order to analyze glycan structures, we performed ELLA on the soluble SOM for the first time and found that it exhibits strong specificity to Datura stramonium lectin (DSL). Furthermore, using biotinylated DSL with anti-biotin antibody conjugated to nanogold, in situ localization of DSL-binding polysaccharides in the P. australiensis skeleton was performed. Signals were distributed on the surfaces of fiber-like crystals of the skeleton, suggesting that polysaccharides may modulate crystal shape. Our study emphasizes the importance of sugar moieties in biomineralization of scleractinian corals.