Bioactive Lyocell Fibers with Inherent Antibacterial, Antiviral and Antifungal Properties.

Functional Lyocell fibers gain interest in garments and technical textiles, especially when equipped with inherently bioactive features. In this study, Lyocell fibers are modified with an ion exchange resin and subsequently loaded with copper (Cu) ions. The modified Lyocell process enables high amounts of the resin additive (>10%) through intensive dispersion and subsequently, high uptake of 2.7% Cu throughout the whole cross-section of the fiber. Fixation by Na2CO3 increases the washing and dyeing resistance considerably. Cu content after dyeing compared to the original fiber value amounts to approx. 65% for reactive, 75% for direct, and 77% for HT dyeing, respectively. Even after 50 household washes, a recovery of 43% for reactive, 47% for direct and 26% for HT dyeing is proved. XRD measurements reveal ionic bonding of Cu fixation inside the cellulose/ion exchange resin composite. A combination of the fixation process with a change in Cu valence state by glucose/NaOH leads to the formation of Cu2O crystallites, which is proved by XRD. Cu fiber shows a strong antibacterial effect against Staphylococcus aureus and Klebsiella pneumonia bacteria, even after 50 household washing cycles of both >5 log CFU. In nonwoven blends with a share of only 6% Cu fiber, a strong antimicrobial (CFU > log 5) and full antiviral effectiveness (>log 4) was received even after 50 washing cycles. Time-dependent measurements already show strong antiviral behavior after 30 s. Further, the fibers show an increased die off of the fungal isolate Candida auris with CFU log 4.4, and nonwovens made from 6% Cu fiber share a CFU log of 1.7. Findings of the study predestines the fiber for advanced textile processing and applications in areas with high germ loads.

Wood inspired biobased nanocomposite films composed of xylans, lignosulfonates and cellulose nanofibers for active food packaging.

The growing concerns on environmental pollution and sustainability have raised the interest on the development of functional biobased materials for different applications, including food packaging, as an alternative to the fossil resources-based counterparts, currently available in the market. In this work, functional wood inspired biopolymeric nanocomposite films were prepared by solvent casting of suspensions containing commercial beechwood xylans, cellulose nanofibers (CNF) and lignosulfonates (magnesium or sodium), in a proportion of 2:5:3 wt%, respectively. All films presented good homogeneity, translucency, and thermal stability up to 153 °C. The incorporation of CNF into the xylan/lignosulfonates matrix provided good mechanical properties to the films (Young's modulus between 1.08 and 3.79 GPa and tensile strength between 12.75 and 14.02 MPa). The presence of lignosulfonates imparted the films with antioxidant capacity (DPPH radical scavenging activity from 71.6 to 82.4 %) and UV barrier properties (transmittance ≤19.1 % (200-400 nm)). Moreover, the films obtained are able to successfully delay the browning of packaged fruit stored over 7 days at 4 °C. Overall, the obtained results show the potential of using low-cost and eco-friendly resources for the development of sustainable active food packaging materials.

Determining monolignol oxifunctionalization by direct infusion electrospray ionization tandem mass spectrometry.

We have successfully developed a validated high-throughput analysis method for the identification and quantification of native and oxifunctionalized monolignols using direct infusion electrospray ionization tandem mass spectrometry (DI-ESI-MS/MS). Oxifunctionalized monolignols generated through unspecific peroxygenase catalysis present a sustainable alternative to fossil aromatic hydrocarbons. This study emphasizes a sustainable analytical approach for these renewable biocatalytic precursors, addressing challenges such as matrix effects, accuracy, precision, and sensitivity of the method. Our findings demonstrate the potential of overcoming quantification difficulties using DI-ESI-MS. Notably, this analytical methodology represents a novel utilization of DI-ESI-MS/MS in examining monolignols and their functionalization, thereby advancing the exploration of lignin as a valuable and sustainable bioresource.

Insights into hydrothermal treatment of biomass blends: Assessing energy yield and ash content for biofuel enhancement.

This study explores the Hydrothermal Carbonization (HTC) treatment of lignocellulosic biomass blends, delving into the influence of several key parameters: temperature, additive nature and dosage, residence time, and biomass composition. Rapeseeds, Pinus radiata sawdust, oat husks, and pressed olive served as the studied biomasses. One hundred twenty-eight experiments were conducted to assess the effects on mass yield (MY), energy yield (EY), higher heating value (HHV), and final ash content (ASH) by a Factorial Experimental Design. The derived model equations demonstrated a robust fit to the experimental data, averaging an R2 exceeding 0.94, affirming their predictive accuracy. The observed energy yield ranged between 65% and 80%, notably with sawdust and olive blends securing EY levels surpassing 70%, while rapeseed blends exhibited the highest HHV at 25 MJ/kg. Temperature emerged as the most influential factor, resulting in an 11% decrease in MY and a substantial 2.20 MJ/kg increase in HHV. Contrastingly, blend composition and additive presence significantly impacted ASH and EY, with all blends exhibiting increased ASH in the presence of additives. Higher initial hemicellulose and aqueous extractive content in raw biomass correlated proportionally with heightened HHV.

Variation pattern in the macromolecular (cellulose, hemicelluloses, lignin) composition of cell walls in Pinus tabulaeformis tree trunks at different ages as revealed using multiple techniques.

The plant cell wall is a complex, heterogeneous structure primarily composed of cellulose, hemicelluloses, and lignin. Exploring the variations in these three macromolecules over time is crucial for understanding wood formation to enhance chemical processing and utilization. Here, we comprehensively analyzed the chemical composition of cell walls in the trunks of Pinus tabulaeformis using multiple techniques. In situ analysis showed that macromolecules accumulated gradually in the cell wall as the plant aged, and the distribution pattern of lignin was opposite that of polysaccharides, and both showed heterogenous distribution patterns. In addition, gel permeation chromatography (GPC) results revealed that the molecular weights of hemicelluloses decreased while that of lignin increased with age. Two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) analysis indicated that hemicelluloses mainly comprised galactoglucomannan and arabinoglucuronoxylan, and the lignin types were mainly comprised guaiacyl (G) and p-hydroxyphenyl (H) units with three main linkage types: ß-O-4, ß-ß, and ß-5. Furthermore, the C-O bond (ß-O-4) signals of lignin decreased while the C-C bonds (ß-ß and ß-5) signals increased over time. Taken together, these findings shed light on wood formation in P. tabulaeformis and lay the foundation for enhancing the processing and use of wood and timber products.

Matrix-free laser desorption/ionization mass spectrometry imaging for rapid evaluation of wood biomass conversion.

RATIONALE: This study overcomes traditional biomass analysis limitations by introducing a pioneering matrix-free laser desorption/ionization (LDI) approach in mass spectrometry imaging (MSI) for efficient lignin evaluation in wood. The innovative acetic acid-peracetic acid (APA) treatment significantly enhances lignin detection, enabling high-throughput, on-site analysis. METHODS: Wood slices, softwood from a conifer tree (Japanese cypress) and hardwood from a broadleaf tree (Japanese beech), were analyzed using MSI with a Fourier transform ion cyclotron resonance mass spectrometer. The developed APA treatment demonstrated effectiveness for MSI analysis of biomass. RESULTS: Our imaging technique successfully distinguishes between earlywood and latewood and enables the distinct visualization of lignin in these and other wood tissues, such as the radial parenchyma. This approach reveals significant contrasts in MSI. It has identified intense ions from ß-O-4-type lignin, specifically in the radial parenchyma of hardwood, highlighting the method's precision and utility in wood tissue analysis. CONCLUSIONS: The benefits of matrix-free LDI include reduced peak overlap, consistent sample quality, preservation of natural sample properties, enhanced analytical accuracy, and reduced operational costs. This innovative approach is poised to become a standard method for rapid and precise biomass evaluation and has important applications in environmental research and sustainable resource management and is crucial for the effective management of diverse biomass, paving the way towards a sustainable, circular society.

Sustainable biorefinery approach by utilizing xylose fraction of lignocellulosic biomass.

Lignocellulosic biomass (LCB) has been a lucrative feedstock for developing biochemical products due to its rich organic content, low carbon footprint and abundant accessibility. The recalcitrant nature of this feedstock is a foremost bottleneck. It needs suitable pretreatment techniques to achieve a high yield of sugar fractions such as glucose and xylose with low inhibitory components. Cellulosic sugars are commonly used for the bio-manufacturing process, and the xylose sugar, which is predominant in the hemicellulosic fraction, is rejected as most cell factories lack the five­carbon metabolic pathways. In the present review, more emphasis was placed on the efficient pretreatment techniques developed for disintegrating LCB and enhancing xylose sugars. Further, the transformation of the xylose to value-added products through chemo-catalytic routes was highlighted. In addition, the review also recapitulates the sustainable production of biochemicals by native xylose assimilating microbes and engineering the metabolic pathway to ameliorate biomanufacturing using xylose as the sole carbon source. Overall, this review will give an edge on the bioprocessing of microbial metabolism for the efficient utilization of xylose in the LCB.

Melt-processable polyvinyl alcohol/lignin composites with improved strength via synergistic plasticization of lignin.

The characteristics of multi-hydroxyl structure and strong hydrogen bonding in polyvinyl alcohol (PVA) make its melting point close to its decomposition temperature, causing melt-processing difficulty. In this work, following the plasticization of small-molecule primary plasticizer acetamide, lignin was demonstrated as a green secondary plasticizer in realizing the melt processing and simultaneous reinforcement of PVA. During the plasticization process, lignin was able to combine with the hydroxyl groups of PVA, so as to destroy the hydrogen bonds and regularity of the PVA chains. The synergistic plasticization effect of lignin dramatically reduced the melting point of PVA from 185 °C to 151 °C. The thermal processing window of PVA composites was expanded from 50 °C to roughly 80 °C after introducing lignin. In contrast to acetamide, the addition of lignin significantly increased the tensile strength and Young's modulus of the composites to 71 MPa and 1.34 GPa, respectively. Meanwhile, lignin helped to hinder the migration of acetamide via hydrogen bonds. With the addition of lignin, the composites also displayed enhanced hydrophobicity and excellent UV shielding performance. The strategy of synergistic plasticization of lignin provides a feasible basis for the practical application of lignin in melt-processable PVA materials with good comprehensive properties.

Understanding the dependence of biochar properties on different types of biomass.

Owing to the diversity of biomasses and many variables in pyrolysis process, the property of biochar from varied biomass feedstock or even same biomass could differ significantly. Since the property of biochar governs the further application of biochar, this review paid particular attention to the correlation between the nature of biomass feedstock and the specifications of biochar in terms of yield, elemental composition, pH, functionalities, heating value, pore structures, morphologies, etc. The property of the biochar from the pyrolysis of cellulose, hemicellulose, lignin, woody biomass (pine, mallee, poplar, acacia, oak, eucalyptus and beech), bark of woody biomass, leaves of woody biomass, straw, algae, fruit peels, tea waste was compared and summarized. In addition, the differences of the biochar of these varied origins were also analyzed. The remaining questions, about the correlation of biomass nature with biochar characteristics, to be further investigated are analyzed in detail. The deduced information about the relationship of the nature of biochar and biomass feedstock as well as key pyrolysis parameters is of importance for further development of the methods for tailoring or production of the biochar of desirable properties. The results from this study could be interesting technically and commercially for the technology developer using biochar as the source of carbon in different applications.

Enhancing the anti-biofouling property of solar evaporator through the synergistic antibacterial effect of lignin and nano silver.

Solar desalination is an effective solution to address the global water scarcity issue. However, biofouling poses a significant challenge for solar evaporators due to the presence of bacteria in seawater. In this study, an anti-biofouling evaporator was constructed using the synergistic antibacterial effect of lignin and silver nanoparticles (AgNPs). The AgNPs were easily synthesized using lignin as reductant under mild reaction conditions. Subsequently, the Lignin-AgNPs solution was integrated into polyacrylamide hydrogel (PAAm) without any purification steps, resulting in the formation of Lignin/AgNPs-PAAm (LAg-PAAm). Under the combined action of AgNPs and the hydroquinone groups present in oxidized lignin, LAg-PAAm achieved over 99 % disinfection efficiency within 1 h, effectively preventing biofilm formation in pore channels of solar evaporators. The anti-biofouling solar evaporator demonstrated an evaporation rate of 1.85 kg m-2 h-1 under 1 sun irradiation, and maintained stable performance for >30 days due to its high efficient bactericidal effect. Furthermore, it also exhibited exceptional salt-rejection capability attributed to its superior hydrophilicity.

High extraction and excellent anti-UV and anti-oxidant proprieties of lignin from Reseda Luteola L. waste by organosolv process.

Lignin is an abundant natural biopolymer found in plant cell walls. Lignin can come from tinctorial plants, whose residual biomass after dye extraction was typically discarded as waste. The main objective of this study was to extract lignin from the residual biomass of Reseda luteola L. using an organosolv process and to optimize the extraction conditions. The extracted lignin was characterized, and its potential applications as an antimicrobial, anti-oxidant, and anti-UV agent were investigated. Response surface methodology based on a Box-Behnken design was employed to optimize the lignin extraction conditions (organic acid concentration, material-to-liquid ratio, extraction time). The extracted lignin was comprehensively characterized using NMR, FTIR, XRD, SEM-EDX, TGA, DSC, and UV-Vis techniques. The optimal extraction conditions yielded a remarkably high lignin recovery of 62.41 % from the plant waste, which was rarely achieved for non-wood plants in previous works. The extracted lignin exhibited excellent thermal stability and radical scavenging anti-oxidant activity but no significant antimicrobial effects. Treating wool fabrics with lignin nanoparticles substantially enhanced UV protection from the "good" to "excellent" category based on the UPF rating. This sustainable valorization approach converted abundant tinctorial plant waste into high-purity lignin with promising anti-oxidant and UV-blocking properties suitable for various applications.

Dimensionally stable and durable wood by lignin impregnation.

Cracking, warping, and decaying stemming from wood's poor dimensional stability and durability are the most annoying issues of natural wood. There is an urgent need to address these issues, of which, sustainable and green chemical treatments are favorably welcomed. Herein, we developed a facile method through the incorporation of environmentally friendly biopolymer lignin into wood cells for wood dimensional stability and durability enhancement. Enzymatic hydrolysis lignin (EHL) was dissolved into various solvents followed by impregnation and drying to incorporate lignin into wood cells. Impregnation treatment was developed to incorporate into wood to improve its dimensional stability, durability, and micromechanics. The anti-swelling efficiency reached up to 99.4 %, the moisture absorption decreased down to 0.55 %, the mass loss after brown rot decay decreased to 7.22 %, and the cell wall elasticity as well as hardness increased 8.7 % and 10.3 %, respectively. Analyses acquired from scanning electron microscopy, fluorescent microscopy, and Raman imaging revealed that the EHL was successfully colonized in cell lumen as well as in cell walls, thus improved wood dimensional stability and durability. Moreover, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed EHL interaction with the cell wall components, thus the wood mechanical property was not impaired significantly, whereas nanoindentation data indicated even slight mechanical enhancement on the cell walls. This facile approach can improve the wood properties in multiple aspects and remarkably enhance the outdoor performance of modified wood products. In addition, using lignin as a natural modifying agent to improve wood performance will have a great positive impact on the environment.

One pot synthesis of furan-modified lignin from agricultural waste via lignin-first approach.

This study investigated a lignin-first approach to produce furan-modified lignin from sugarcane bagasse (SB), rice hull (RH), and sunn hemp biomass (SHB) using 5 methylfurfural (MF) and 5 methul-2-furanmethanol (MFM). The reaction time (5 h) was selected based on the delignification of SB using methanol and Ru/C catalyst which yielded the highest hydroxyl content. Delignification of SB with various MF weight ratios (1:1, 1:2, 1:3, 2:1, and 3:1) revealed that 1:1 and 2:1 ratios produced the highest hydroxyl content (7.7 mmol/g) and bio-oil yield (23.2 % wt% total weight). Further exploration identified that RH and MF at 1:1 ratio and SHB and MF at a 2:1 ratio produced the highest hydroxyl content (13.0 mmol/g) and bio-oil yield (31.6 % wt% tot. weight). This study developed a one-step method to extract and modify lignin with furan compounds simultaneously while opening new avenues for developing value-added products.

Integration of lactic acid biorefinery with treatment of red mud from alumina refinery: win-win paradigm for waste valorization.

The cost of detoxification and neutralization poses certain challenges to the development of an economically viable lactic acid biorefinery with lignocellulosic biomass as feedstock. Herein, red mud, an alkaline waste, was explored as both a detoxifying agent and a neutralizer. Red mud treatment of lignocellulosic hydrolysate effectively removed the inhibitors generated in dilute acid pretreatment, improving the lactic acid productivity from 1.0 g/L·h-1 to 1.9 g/L·h-1 in later fermentation. In addition, red mud could replace CaCO3 as a neutralizer in lactic acid fermentation, which in turn enabled simultaneous bioleaching of valuable metals (Sc, Y, Nd, and Al) from red mud. The neutralization of alkali in red mud by acids retained in lignocellulosic hydrolysate and lactic acid produced from fermentation led to effective dealkalization, rendering a maximum alkali removal efficiency of 92.2 %. Overall, this study offered a win-win strategy for the valorization of both lignocellulosic biomass and red mud.

miR397 regulates cadmium stress response by coordinating lignin polymerization in the root exodermis in Kandelia obovata.

Secondary lignification of the root exodermis of Kandelia obovata is crucial for its response to adversity such as high salinity and anaerobic environment, and this lignification is also effective in blocking cadmium transport to the roots. However, how the differences in lignification of root exodermis at different developmental stages respond to Cd stress and its regulatory mechanisms have not been revealed. In this study, after analyzing the root structure and cell wall thickness using a Phenom scanning electron microscope as well as measuring cadmium content in the root cell wall, we found that the exodermis of young and mature roots of K. obovata responded to Cd stress through the polymerization of different lignin monomers, forming two different mechanisms: chelation and blocking. Through small RNA sequencing, RLM-5'-RACE and dual luciferase transient expression system, we found that miR397 targets and regulates KoLAC4/17/7 expression. The expression of KoLAC4/17 promoted the accumulation of guaiacyl lignin during lignification and enhanced the binding of cadmium to the cell wall. Meanwhile, KoLAC7 expression promotes the accumulation of syringyl lignin during lignification, which enhances the obstruction of cadmium and improves the tolerance to cadmium. These findings enhance our understanding of the molecular mechanisms underlying the differential lignification of the root exodermis of K. obovata in response to cadmium stress, and provide scientific guidance for the conservation of mangrove forests under heavy metal pollution.

Isolation and chemical characterization of lignocellulosic fiber from Pueraria montana using Box-Behnken design for weed management.

The huge demand for natural fibers necessitates the search for non-traditional bioresources including invasive species which are deteriorating the ecosystem and biodiversity. The study aims to utilize Pueraria montana weed for the extraction of lignocellulosic fiber using both traditional (water retting) and chemical extraction methods to determine the better extraction method. Chemically extracted fiber showed 17.09 g/tex bundle strength whereas water-extracted fiber showed 11.7 g/tex bundle strength. Therefore, chemical extraction method was chosen for fiber isolation by optimization of reaction conditions using Box Behnken Design. Based on the design, optimal conditions obtained were 1 % w/v NaOH, 0.75 % v/v H2O2, and 3 days retting time. Solid-state NMR illustrated the breakdown of hemicellulose linkages at 25.89 ppm. FTIR revealed the disappearance of C=O groups of hemicellulose at 1742 cm-1. TGA demonstrated thermal stability of chemically treated fiber up to 220 °C and activation energy of 60.122 KJ/mol. XRD evidenced that chemically extracted fiber has a crystallinity index of 71.1 % and a crystal size of 2 nm. Thus P. montana weed holds potential for the isolation of natural fiber as its chemical composition and properties are comparable to commercial lignocellulosic fibers. The study exemplifies the transformation of weed to a bioresource of natural fibers.

Sodium lignosulfonate/graphene composites for efficient desalination by incorporating CoS to control pore size.

The phenomenon of overlapping double layers due to micropores inhibits capacitive deionization performance, which is improved by increasing the pore size. In this study, a novel ternary composite electrode (sodium lignosulfonate/reduced graphene oxide/cobalt sulfide, LGC) was designed using a two-step hydrothermal method. CoS with high pseudocapacitance modifies sodium lignosulfonate and graphene connected by hydrogen bonding, benefiting from the constitutive steric structure. The electrochemical performance was significantly enhanced, and the desalination capacity substantially improved. The LGC electrode specific capacitance was as high as 354.47 F g-1 at a 1 A g-1 current density. The desalination capacity of the capacitive deionization device comprising LGC and activated carbon in 1 M NaCl electrolyte reached 28.04 mg g-1 at an operating condition of 1.2 V, 7 mL min-1. Additionally, the LGC electrodes degraded naturally post the experiment by simply removing the CoS, suggesting that the LGC composites are promising material for capacitive deionization electrodes.

Oleic acid decorated kraft lignin as a hydrophobic and functional filler of cellulose acetate films.

The packaging industry has primarily been dominated by single-use, petrochemical-sourced plastic materials despite their short-term use. Their leakage into the ecosystem after their use poses substantial environmental concerns. As a result, compostable and renewable packaging material alternatives are garnering significant attention. Cellulose acetate is a derivative of cellulose that exhibits excellent tensile properties, transparency, melt processability, and intermediate compostability. However, its application in the food packaging industry is limited due to its hygroscopic behavior and lack of dimensional stability. This study investigated using lignin (pristine and esterified) as a functional additive of cellulose acetate. The effect of varying concentrations of pristine kraft and oleic acid functionalized lignin in the cellulose acetate matrix and its effect on the resulting film's mechanical, morphological, viscoelastic, and water barrier properties were explored. Comprehensive characterization of the thermomechanical processed lignin-cellulose acetate sheets revealed reduced moisture absorption, improved UV and moisture barrier, and enhanced tensile properties with melt processability. Overall, the studied films could have appealing properties for food and other packaging applications, thus, serving as eco-friendly and sustainable alternatives to conventional petroleum-derived packing materials.

Temporal dynamics of lignin degradation in Quercus acutissima sawdust during Ganoderma lucidum cultivation.

Despite a fair amount of lignin conversion during mycelial growth, previous structural analyses have not yet revealed how lignin changes continuously and what the relationship is between lignin and ligninolytic enzymes. To clarify these aspects, Quercus acutissima sawdust attaching Ganoderma lucidum mycelium collected from different growth stage was subjected to analysis of lignin structure and ligninolytic enzyme activity. Two key periods of lignin degradation are found during the cultivation of G. lucidum: hypha rapid growth period and primordium formation period. In the first stage, laccase activity is associated with the opening of structures such as methoxyls, ß-O-4' substructures and guaiacyl units in lignin, as well as the shortening of lignin chains. Manganese peroxidases and lignin peroxidases are more suitable for degrading short chain lignin. The structure of phenylcoumarans and syringyl changes greatly in the second stage. The results from sawdust attaching mycelium provide new insights to help improve the cultivation substrate formulation of G. lucidum and understand biomass valorization better.

Fenton-ultrasound treatment of corn stalks enhances humification during composting by stimulating the inheritance and synthesis of polyphenolic compounds-preliminary evidence from a laboratory trial.

The impact of Fenton-ultrasound treatment on the production of polyphenols and humic acid (HA) during corn stalk composting was investigated by analyzing the potential for microbial assimilation of polysaccharides in corn stalks to generate polyphenols using a13C-glucose tracer. The results showed that Fenton-ultrasound treatment promoted the decomposition of lignocellulose and increased the HA content, degree of polymerization (DP), and humification index (HI). The primary factor could be attributed to Fenton-ultrasound treatment-induced enhanced the abundance of lignocellulose-degrading microorganisms, as Firmicutes, Actinobacteria phylum and Aspergillis genus, which serve as the primary driving forces behind polyphenol and HA formation. Additionally, the utilization of a13C isotope tracer revealed that corn stalk polysaccharide decomposition products can be assimilated by microbes and subsequently secrete polyphenolic compounds. This study highlights the potential of microbial activity to generate phenolic compounds, offering a theoretical basis for increasing polyphenol production and promoting HA formation during composting.