Lignin and functional polymer-based materials: Synthesis, characterization and application for Cr (VI) and As (V) removal from aqueous media.

In this study, lignin derived from corncobs was chemically modified by substituting the hydroxyl groups present in its structure with methacrylate groups through a catalytic reaction using methacrylic anhydride, resulting in methacrylated lignin (ML). These MLs were incorporated in polymerization reaction of the monomer 2-[(acryloyloxy)ethyl trimethylammonium] chloride (Cl-AETA) and Cl-AETA, Cl-AETA/ML polymers were obtained, characterized (spectroscopic, thermal and microscopic analysis), and evaluated for removing Cr (VI) and As (V) from aqueous media in function of pH, contact time, initial metal concentrations and adsorbent amount. The Cl-AETA/ML polymers followed the Langmuir adsorption model for the evaluated metal anions and were able to remove up to 91 % of Cr (VI) with a qmax (maximum adsorption capacity) of 201 mg/g, while for As (V), up to 60 % could be removed with a qmax of 58 mg/g. The results demonstrate that simple modifications in lignin enhance its functionalization and properties, making it suitable for removing contaminants from aqueous media, showing promising results for potential future applications.

Sodium lignosulfonate as an extracting agent of methylene blue dye using a polymer-enhanced ultrafiltration technique.

The purpose of this research was to evaluate the efficacy of sodium lignosulfonate (LS) as a dye adsorbent in the removal of methylene blue (MB) from water by polymer-enhanced ultrafiltration. Various parameters were evaluated, such as membrane molecular weight cut-off, pH, LS dose, MB concentration, applied pressure, and the effect of interfering ions. The results showed that the use of LS generated a significant increase in MB removal, reaching an elimination of up to 98.0 % with 50.0 mg LS and 100 mg L-1 MB. The maximum MB removal capacity was 21 g g-1 using the enrichment method. In addition, LS was reusable for up to four consecutive cycles of dye removal-elution. The removal test in a simulated liquid industrial waste from the textile industry was also effective, with a MB removal of 97.2 %. These findings indicate that LS is highly effective in removing high concentrations of MB dye, suggesting new prospects for its application in water treatment processes.

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.

Lignin degradation by a novel thermophilic and alkaline yellow laccase from Chitinophaga sp.

Laccases (EC 1.10.3.2) are oxidoreductases that belong to the multicopper oxidase subfamily and are classified as yellow/white or blue according to their absorption spectrum. Yellow laccases are more useful for industrial processes since they oxidize nonphenolic compounds in the absence of a redox mediator and stand out for being more stable and functional under extreme conditions. This study aimed to characterize a new laccase that was predicted to be present in the genome of Chitinophaga sp. CB10 - Lac_CB10. Lac_CB10, with a molecular mass of 100.06 kDa, was purified and characterized via biochemical assays using guaiacol as a substrate. The enzyme demonstrated extremophilic characteristics, exhibiting relative activity under alkaline conditions (CAPS buffer pH 10.5) and thermophilic conditions (80-90°C), as well as maintaining its activity above 50% for 5 h at 80°C and 90°C. Furthermore, Lac_CB10 presented a spectral profile typical of yellow laccases, exhibiting only one absorbance peak at 300 nm (at the T2/T3 site) and no peak at 600 nm (at the T1 site). When lignin was degraded using copper as an inducer, 52.27% of the material was degraded within 32 h. These results highlight the potential of this enzyme, which is a novel yellow laccase with thermophilic and alkaline activity and the ability to act on lignin. This enzyme could be a valuable addition to the biorefinery process. In addition, this approach has high potential for industrial application and in the bioremediation of contaminated environments since these processes often occur at extreme temperatures and pH values. IMPORTANCE: The characterization of the novel yellow laccase, Lac_CB10, derived from Chitinophaga sp. CB10, represents a significant advancement with broad implications. This enzyme displays exceptional stability and functionality under extreme conditions, operating effectively under both alkaline (pH 10.5) and thermophilic (80-90°C) environments. Its capability to maintain considerable activity over extended periods, even at high temperatures, showcases its potential for various industrial applications. Moreover, its distinctive ability to efficiently degrade lignin-demonstrated by a significant 52.27% degradation within 32 h-signifies a promising avenue for biorefinery processes. This newfound laccase's characteristics position it as a crucial asset in the realm of bioremediation, particularly in scenarios involving contamination at extreme pH and temperature levels. The study's findings highlight the enzyme's capacity to address challenges in industrial processes and environmental cleanup, signifying its vital role in advancing biotechnological solutions.

Green Flame-Retardant Blend Used to Improve the Antiflame Properties of Polypropylene.

The flammability properties of polymers and polymeric composites play an important role in ensuring the safety of humans and the environment; moreover, flame-retardant materials ensure a greater number of applications. In the present study, we report the obtaining of polypropylene (PP) composites contain a mixture of two green flame retardants, lignin and clinoptilolite, by melt extrusion. These additives are abundantly found in nature. Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), mechanical properties, scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), cone calorimetry, UL-94, and carbonized residues analysis were carried out. TGA analysis shows that PPGFR-10 and PPGFR-20 compounds presented better thermal stability with respect to PP without flame retardants. The conical calorimetric evaluation of the composites showed that PPGFR-10 and PPGFR-20 presented decreases in peak heat release rates (HRRs) of 9.75% and 11.88%, respectively. The flammability of the composites was evaluated with the UL-94 standard, and only the PPGFR-20 composite presented the V-0 and 5VB classification, which indicates good flame-retardant properties. Additives in the polymer matrix showed good dispersion with few agglomerates. The PPGFR-20 composite showed an FRI value of 1.15, higher percentage of carbonized residues, and UL-94 V-0 and 5VB rating, suggesting some kind of synergy between lignin and clinoptilolite, but only at high flame-retardant concentrations.

Biochemical changes, metal content, and spectroscopic analysis in sewage sludge composted with lignocellulosic residue using FTIR-MIR and FTIR-NIR.

The use of lignocellulosic residues, originating from sawdust, in composting sewage sludge for organic fertilizer production, is a practice of growing interest. However, few studies have explored the effect of the proportion of sawdust and sewage sludge raw materials on composting performance in the humification process. This study assessed the addition of sawdust in the sewage sludge composting process, regarding carbon content, presence of heavy metals, and humification of the organic compost. The experimental design employed was a randomized complete block design with five treatments featuring different proportions of organic residues to achieve C/N ratios between 30-1 (T1: 100% sewage sludge and 0% sawdust, T2: 86% sewage sludge and 14.0% sawdust, T3: 67% sewage sludge and 33% sawdust, T4: 55% sewage sludge and 45% sawdust, and T5: 46.5% sewage sludge and 53.5% sawdust) and five replications, totaling 25 experimental units. The addition of lignocellulosic residue in sewage sludge composting increased the levels of TOC and the C/N ratio, reduced the levels of pH, P, N, Na, Ba, and Cr, and did not interfere with the levels of K, Ca, Mg, S, CEC, labile carbon, and metals Fe, Zn, Cu, Mn, Ni, and Pb. The increase in the proportion of sawdust residue favored the degradation of aliphatic groups, increasing the presence of aromatic structures and reducing humification at the end of composting. The use of sawdust as a lignocellulosic residue in sewage sludge composting is a viable and efficient alternative to produce high-quality organomineral fertilizers.

Co-composting of green waste and biogas waste: physical, chemical parameters and quality of ripe compound.

The impact of adding biogas waste (BW) to green waste (GW) composting to increase nitrogen supplementation and improve mature compost quality was investigated. Conducted over 90 days using static windrows, the experiment compared treatments with GW alone (T1) and GW supplemented with BW (T2 and T3). The results showed that the addition of BW increased temperatures, improved the C/N ratio, and expedited the stabilization process compared to T1. Furthermore, the addition of BW led to significant degradation of hemicellulose (up to 39.98%) and cellulose (up to 27.63%) compared to GW alone. Analysis of Fourier-transform infrared (FTIR) spectra revealed the presence of aromatic, phenolic, aliphatic, and polysaccharide structures in the compost, with BW supplementation enhancing these characteristics. Importantly, the germination index (GI) assessment indicated that the compounds produced were not toxic and instead exhibited stimulatory effects on seed germination. Overall, the findings suggest that supplementing GW composting with BW can enhance the quality and efficacy of the composting process, resulting in compost with desirable properties for agricultural use.

Role of Nb2O5 Crystal Phases on the Photocatalytic Conversion of Lignin Model Molecules and Selectivity for Value-Added Products.

The photocatalytic conversion in aqueous media of phenol and guaiacol as a lignin model compound using Nb2O5 with different crystal phases was studied. Nb2O5 particles were synthesized using hydrothermal methods, where it was observed that changes in the solvent control their morphology and crystal phase. Different photocatalytic behavior of Nb2O5 was observed with the selected model compounds, indicating that its selection directly impacts the resulting conversion and selectivity rates as well as the reaction pathway, highlighting the relevance of model molecule selection. Photocatalytic conversion of phenol showed conversion rate (C%) up to 25 % after 2 h irradiation and high selectivity (S%) to pyrogallol (up to 50 %). Orthorhombic Nb2O5 spheres favored conversion through free hydroxyl radicals while monoclinic rods did not convert phenol. Guaiacol photocatalytic oxidation showed high conversion rate but lower selectivity. Orthorhombic and monoclinic Nb2O5 favored the formation of resorcinol with S % ~0.43 % (C % ~33 %) and ~13 % (C % ~27 %) respectively. The mixture of both phases enhanced the guaiacol conversion rate to ~55 % with ~17 % of selectivity to salicylaldehyde. The use of radical scavengers provided information to elucidate the reaction pathway for these model compounds, showing that different reaction pathways may be obtained for the same photocatalyst if the model compound is changed.

Caatinga, Amazon and Atlantic Forest as natural sources for microbial lignocellulolytic enzymes.

Brazilian biomes are important sources for environmental microorganisms, including efficient metabolic machineries, like actinomycetes. These bacteria are known for their abilities to produce many bioactive compounds, including enzymes with multiple industrial applications. The present work aimed to evaluate lignocellulolytic abilities of actinomycetes isolated from soil and rhizosphere samples collected at Caatinga, Atlantic and Amazon Forest. Laccase (Lac), lignin peroxidase (LiP), manganese peroxidase (MnP) and cellulase were evaluated for their efficiency. These enzymes have an essential role in lignin decomposition, through oxidation of phenolic and non-phenolic compounds, as well as enzymatic hydrolysis of vegetal biomass. In this sense, a total of 173 actinomycetes were investigated. Eleven (11) of them were selected by their enzymatic performance. The actinomycete AC166 displayed some activity in all analysed scenarios in terms of Lac, MnP and LiP activity, while AC171 was selected as the most promising strain, showing the following activities: 29.7 U.L-1 for Lac; 2.5 U.L-1 for LiP and 23 U.L-1 for MnP. Cellulolytic activities were evaluated at two pH conditions, 4.8 and 7.4, obtaining the following results: 25 U.L-1 and 71 U.L-1, respectively. Thermostability (4, 30 and 60 o C) and salinity concentrations (0 to 4 M) and pH variation (2.0 to 9.0) stabilities of the obtained LiP and Lac enzymatic extracts were also verified. The actinomycete strain AC171 displayed an adaptable response in distinct pH and salt profiles, indicating that bacterial LiP was some halophilic type. Additionally, the strain AC149 produced an alkali and extreme halophilic lignin peroxidase, which are promising profiles for their future application under lignocellulosic biomass at bioethanol biorefineries.

Side-stream lignins: Potential antioxidant and antimicrobial agents in milk.

In recent years, lignin has drawn increasing attention due to its intrinsic antibacterial and antioxidant activities, biodegradability, and biocompatibility. Yet, like several other biogenic structures, its compositional heterogeneity represents a challenge to overcome. In addition, there are few studies regarding food applications of lignin. Herein, we evaluate the antimicrobial and antioxidant effects of lignin from two different sources. These lignins were characterized by attenuated total reflectance Fourier-transform infrared (ATR-FTIR) and hydrogen nuclear magnetic resonance (1H NMR) spectroscopies. Their antibacterial and antioxidant capacities (DPPH and Folin-Ciocalteu methods) were also investigated. Susceptibility tests were performed with the minimal inhibitory (MIC) and bactericidal (MBC) concentrations using the micro-broth dilution technique. Kraft lignin presented higher radical-scavenging and antibacterial activities than alkali lignin, indicating the dependence of antioxidant and antibacterial activities on the precursor biomass. Scanning electron microscopy shows morphologic changes in the bacteria after exposure to lignin, while confocal microscopy suggests that kraft lignin has affinity towards bacterial surfaces and the ability to cause cell membrane destabilization. Lignin inhibited the growth of Staphylococcus aureus and Salmonella Enteritidis in skimmed milk, herein taken as food model. Our results suggest that lignins are promising candidates for green additives to improve quality and safety within the food chain.

Modulating the properties and structure of lignins produced by alkaline delignification of sugarcane bagasse pretreated with two different mineral acids at pilot-scale.

Sugarcane bagasse was pretreated with dilute phosphoric acid or sulfuric acid to facilitate cellulose hydrolysis and lignin extraction. With phosphoric acid, only 8 % of the initial cellulose was lost after delignification, whereas pretreatment with sulfuric acid resulted in the solubilization of 38 % of the initial cellulose. After enzymatic hydrolysis, the process using phosphoric acid produced approximately 35 % more glucose than that using sulfuric acid. In general, the lignins showed 95-97 % purity (total lignin, w/w), an average molar mass of 9500-10,200 g mol-1, a glass transition temperature of 140-160 °C, and a calorific value of 25 MJ kg-1. Phosphoric acid lignin (PAL) was slightly more polar than sulfuric acid lignin (SAL). PAL had 13 % more oxidized units and 20 % more OH groups than SAL. Regardless of the acid used, the lignins shared similar properties, but differed slightly in the characteristics of their functional groups and chemical bonds. These findings show that pretreatment catalyzed with either of the two acids resulted in lignin with sufficiently good characteristics for use in industrial processes.

Effects of leaf and stem maturation on nutritional value in Megathyrsus maximus.

BACKGROUND: Megathyrsus maximus is a forage grass native to Africa but widely cultivated in tropical and subtropical regions of the world where it is part of the grazing food chain. This study aimed to evaluate five M. maximus genotypes for the effect of maturity on their morpho-agronomic traits, nutritional composition and digestibility, and to correlate their leaf blade and stem anatomy with their nutritional value. RESULTS: The proportion of sclerenchyma tissues increased as maturity was reached, while lignin accumulation was differentiated between genotypes. Gatton Panic, Green Panic and Mutale genotypes maintained their acid detergent lignin (ADL) values for leaf blades in the three cuts evaluated. In sacco ruminal dry matter disappearance was lower in Green Panic genotype at the vegetative stage for stems, but not for leaf blades. Significant positive correlations were found between dry matter disappearance and mesophyll tissues, and the latter were negatively correlated with neutral detergent fiber (NDF) and ADL. CONCLUSION: Our results strongly indicate that cutting age and genotype affected the nutritional value of M. maximus leaf blades and stems, with a more pronounced loss of quality in stems than in leaf blades. We recommend increasing the frequency of grazing at early stage or anticipating the stage of stem elongation in Green Panic to produce forage with better nutritional value. © 2023 Society of Chemical Industry.

Development of a rapid assay for ß-etherase activity using a novel chromogenic substrate.

Biocatalytic processes play a crucial role in the valorization of lignin; therefore, methods enabling the monitoring of enzymes such as ß-etherases, capable of breaking ß-O-4 aryl-ether bonds, are of significant biotechnological interest. A novel method for quantifying ß-etherase activity was developed based on the ß-ester bond formation between a chromophore and acetovainillone. The chromogenic substrate ß-(ρ-nitrophenoxy)-α-acetovanillone (PNPAV), was chemically synthesized. Kintetic monitoring of ρ-nitrophenolate release at 410 nm over 10 min, using recombinant LigF from Sphingobium sp SYK-6, LigF-AB and LigE-AB from Althererytrobacter sp B11, yielded enzimatic activities of 404. 3 mU/mg, 72 mU/mg, and 50 mU/mg, respectively. This method is applicable in a pH range of 7.0-9.0, with a sensitivity of up to 50 ng of enzyme, exhibiting no interference with lipolytic, glycolytic, proteolytic, and oxidoreductase enzymes.

Production of highly antioxidant lignin nanoparticles from a hardwood technical lignin.

Eucalypt kraft lignin isolated in a LignoBoost™ pilot plant was characterized by GC-MS, ICP-OES, DSC, HPSEC, 31P NMR, and HSQC 2D-NMR to be used without any further processing to produce lignin nanoparticles (LNPs) by nanoprecipitation. Tetrahydrofuran (THF) was used as a solvent, and water as a non-solvent. Microscopic analysis (TEM) showed that LNPs were regularly spherical with some hollow particles dispersed in-between, and sizes were tunable by changing the solvent dripping rate onto the non-solvent. LNP particle sizes had a bimodal distribution, with the largest population having an average apparent hydrodynamic diameter ranging from 105.6 to 75.6 nm. Colloidal dispersions of LNPs in water presented good stability in different dilutions without significant size changes upon storage at pH close to neutral for as long as 45 days. Zeta potentials around -40 mV were obtained for LNP suspensions at pH ranging from 7 to 9. The high carbohydrate content (circa 10 % on a dry basis, mostly xylans) of the lignin precursor did not interfere in LNP formation, whose antioxidant activity was expressive as demonstrated by the ABTS assay at pH 7.4, with an EC50 of 4.04 µg mL-1. Also, the Trolox® equivalent antioxidant capacity (TEAC) of LNPs reached 1.90 after 40 min reaction time.

Lignin Analysis by HPLC and FTIR: Spectra Deconvolution and S/G Ratio Determination.

Fourier transform infrared spectroscopy (FTIR) is a simple nondestructive technique that allows the user to obtain quick and accurate information about the structure of the constituents of wood. Spectra deconvolution is a computational technique, complementary to FTIR analysis, which improves the resolution of overlapped or unobserved bands in the raw spectra. High performance liquid chromatography (HPLC) is an analytical technique useful to determine the ratio of the lignin monomers obtained by the alkaline nitrobenzene oxidation method. Furthermore, lignin content has been commonly determined by wet chemical methods; Klason lignin determination is a quick and accessible method. Here, we detail the procedures for chemical analysis of the wood lignin using these techniques. Additionally, the deconvolution process of FTIR spectra for the determination of the S/G ratio, in lignin isolated by this or other methods, is explained in detail.

Cloning, expression, and biochemical characterization of ß-etherase LigF from Altererythrobacter sp. B11.

Lignin, a complex heteropolymer present in plant cell walls, is now recognized as a valuable renewable resource with potential applications in various industries. The lignin biorefinery concept, which aims to convert lignin into value-added products, has gained significant attention in recent years. ß-etherases, enzymes that selectively cleave ß-O-4 aryl ether bonds in lignin, have shown promise in lignin depolymerization. In this study, the ß-etherase LigF from Altererythrobacter sp. B11 was cloned, expressed, purified, and biochemically characterized. The LigF-AB11 enzyme exhibited optimal activity at 32 °C and pH 8.5 when catalyzing the substrate PNP-AV. The enzyme displayed mesophilic behavior and demonstrated higher activity at moderate temperatures. Stability analysis revealed that LigF-AB11 was not thermostable, with a complete loss of activity at 60 °C within an hour. Moreover, LigF-AB11 exhibited excellent pH stability, retaining over 50 % of its activity after 1 h under pH conditions ranging from 3.0 to 11.0. Metal ions and surface impregnation agents were found to affect the enzyme's activity, highlighting the importance of considering these factors in enzymatic processes for lignin depolymerization. This study provides valuable insights into the biochemical properties of LigF-AB11 and contributes to the development of efficient enzymatic processes for lignin biorefineries. Further optimization and understanding of ß-etherases will facilitate their practical application in the valorization of lignin.

Obtaining of a rich-cellulose material from black wattle (Acacia mearnsii De Wild.) bark residues.

Black wattle (Acacia mearnsii De Wild.) barks are residues produced by tannin industries in huge quantities, which are normally discharged on environmental or used for energy production. Therefore, this study aimed to evaluate the use of black wattle bark residues as a raw material on obtaining of a rich-cellulose material by alkaline (MET1), acetosolv (MET2), and organosolv (MET3) procedures. The results obtained indicated that the alkaline methodology, followed by a bleaching step (MET1), promoted klason lignin and hemicellulose removals more efficiently. It was possible to observe that better results were achieved using NaOH concentration of 6% (wt%), at 65 °C for 2.5 h, presenting a yield of 63.24 ± 1.25%, and a reduction on klason lignin content of almost 90.45%. Regarding the bleaching step, it was possible to obtain a material free of non-cellulosic compounds with a yield of 78.28 ± 1.48%. Thermogravimetric analysis indicated the removal of lignin and hemicellulose as well as an increase in cellulose degradation temperature, due to changes in crystalline phases. According to X-ray diffraction (XRD), the procedures employed have led to an increase in crystallinity from 66.27 to 91.78% due to the removal of non-cellulosic compounds. Scanning electron microscopy (SEM) showed morphological alterations in accordance with the removal of non-cellulosic compounds.

Nanosilica enhances morphogenic and chemical parameters of Megathyrsus maximus grass under conditions of phosphorus deficiency and excess stress in different soils.

Phosphorus (P) imbalances are a recurring issue in cultivated soils with pastures across diverse regions. In addition to P deficiency, the prevalence of excess P in soil has escalated, resulting in damage to pasture yield. In response to this reality, there is a need for well-considered strategies, such as the application of silicon (Si), a known element for alleviating plant stress. However, the influence of Si on the morphogenetic and chemical attributes of forage grasses grown in various soils remains uncertain. Consequently, this study aimed to assess the impact of P deficiency and excess on morphogenetic and chemical parameters, as well as digestibility, in Zuri guinea grass cultivated in Oxisol and Entisol soils. It also sought to determine whether fertigation with nanosilica could mitigate the detrimental effects of these nutritional stresses. Results revealed that P deficiency led to a reduction in tiller numbers and grass protein content, along with an increase in lignin content. Conversely, P excess resulted in higher proportions of dead material and lignin, a reduced mass leaf: stem ratio in plants, and a decrease in dry matter (DM) yield. Fertigation with Si improved tillering and protein content in deficient plants. In the case of P excess, Si reduced tiller mortality and lignin content, increased the mass leaf:stem ratio, and enhanced DM yield. This approach also increased yields in plants with sufficient P levels without affecting grass digestibility. Thus, Si utilization holds promise for enhancing the growth and chemical characteristics of forage grasses under P stress and optimizing yield in well-nourished, adapted plants, promoting more sustainable pasture yields.

Catalytic Selective Oxidation of ß-O-4 Bond in Phenethoxybenzene as a Lignin Model Using (TBA)5[PMo10V2O40] Nanocatalyst: Optimization of Operational Conditions.

The catalytic oxidation of phenethoxybenzene as a lignin model compound with a ß-O-4 bond was conducted using the Keggin-type polyoxometalate nanocatalyst (TBA)5[PMo10V2O40]. The optimization of the process's operational conditions was carried out using response surface methodology. The statistically significant variables in the process were determined using a fractional factorial design. Based on this selection, a central circumscribed composite experimental design was used to maximize the phenethoxybenzene conversion, varying temperature, reaction time, and catalyst load. The optimal conditions that maximized the phenethoxybenzene conversion were 137 °C, 3.5 h, and 200 mg of catalyst. In addition, under the optimized conditions, the Kraft lignin catalytic depolymerization was carried out to validate the effectiveness of the process. The depolymerization degree was assessed by gel permeation chromatography from which a significant decrease in the molar mass distribution Mw from 7.34 kDa to 1.97 kDa and a reduction in the polydispersity index PDI from 6 to 3 were observed. Furthermore, the successful cleavage of the ß-O-4 bond in the Kraft lignin was verified by gas chromatography-mass spectrometry analysis of the reaction products. These results offer a sustainable alternative to efficiently converting lignin into valuable products.

Unveiling the mechanistic aspects of methylene blue adsorption onto a novel phosphate-decorated coconut fiber lignin.

The aim of this work was to evaluate the adsorptive performance of the phosphorylated coconut fiber lignin (PCFL) obtained through an innovative biorefinery process for removing methylene blue (MB). PCFL was obtained using coconut fiber mixed with 85 % wt. H3PO4 at 70 °C for 1 h. Milled wood lignin (MWL) and PCFL were characterized by FTIR, CP-MAS 31P NMR, phosphorous and hydroxyl contents, pHPZC, and BET analyses. The batch adsorption tests evaluated the effects of the biosorbent (0.25 - 4 g L-1) and adsorbate dosages (2.5 - 7.5 mg L-1), contact time (0 - 60 min), pH (4 - 8), ionic strength (0.001 - 0.1 mol L-1) and temperature (298.15 - 318.15 K) on MB adsorption. Kinetic, equilibrium, and thermodynamic modeling were used. The phosphorous content on PCFL was 2.5 times higher than that of MWL. PCFL presented an enhanced adsorptive performance for removing MB, which was spontaneous (ΔG0 < 0), endothermic (ΔH0 > 0), with affinity between the biosorbent and adsorbate (ΔS0 > 0), and driven by physisorption (Ea > 40 kJ mol-1). The adsorptive performance of PCFL was enhanced due to the grafting of new active sites by using an innovative biorefinery process, showing its potential to be used for textile effluent remediation.