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.

High-performance acetosolv lignin-incorporated DGEBA cured with aprotic imidazolium-based ionic liquid: Polymerization, chemical, thermal and combustion aspects of the thermosetting materials.

The lignin valorization constitutes a chemical platform for several segments of chemical industry. The aim of this work was to evaluate the potential of acetosolv coconut fiber lignin (ACFL) as an additive to DGEBA, curing it using an aprotic IL ([BMIM][PF6]) and analyze the properties of the obtained thermosetting materials. ACFL was obtained by mixing coconut fiber with 90 % acetic acid and 2 % HCl at 110 °C during 1 h. ACFL was characterized by FTIR, TGA and 1H NMR. The formulations were fabricated by mixing DGEBA and ACFL at different concentrations (0-50 % wt.). The curing parameters and [BMIM][PF6] concentrations were optimized by DSC analyses. The cured ACFL-incorporated epoxy resins were characterized by gel content (GC), TGA, MCC and chemical resistance in different media. ACFL undergone a selective partial acetylation that favored its miscibility with DGEBA. High GC values were obtained at high curing temperatures and ACFL concentration. The crescent ACFL concentration did not affect the Tonset of the thermosetting materials significantly. ACFL has increased the resistance of DGEBA to combustion and different chemical media. ACFL has shown a great potential to be used as a bio-additive for enhancing the chemical, thermal and combustion properties of high-performance materials.

Development of a phosphorous-based biorefinery process for producing lignocellulosic functional materials from coconut wastes.

This work aimed to develop a phosphorous-based biorefinery process for obtaining phosphorylated lignocellulosic fractions in a one-pot protocol from coconut fiber. Natural coconut fiber (NCF) was mixed with 85 % m/m H3PO4 at 70 °C for 1 h to yield the modified coconut fiber (MCF), aqueous phase (AP), and coconut fiber lignin (CFL). MCF was characterized by its TAPPI, FTIR, SEM, EDX, TGA, WCA, and P content. AP was characterized regarding its pH, conductivity, glucose, furfural, HMF, total sugars and ASL contents. CFL structure was evaluated by FTIR, 1H, 31P and 1H-13C HSQC NMR, TGA and P content and was compared to that of milled wood lignin (MWL). It was observed that MCF and CFL were phosphorylated during the pulping (0.54 and 0.23 % wt., respectively), while AP has shown high sugar levels, low inhibitor content, and some remaining phosphorous. The phosphorylation of MCF and CFL also showed an enhancement of their thermal and thermo-oxidative properties. The results show that a platform of functional materials such as biosorbents, biofuels, flame retardants, and biocomposites can be created through an eco-friendly, simple, fast, and novel biorefinery process.

Unraveling the adsorption mechanism of methylene blue onto selective pH precipitated Kraft lignins: Kinetic, equilibrium and thermodynamic aspects.

Lignin has been used on its crude or modified forms for adsorption purposes. This work evaluated the influence of selective pH precipitation of Kraft lignins (KLs) on their adsorptive performance for removing methylene blue (MB). The alkaline and acid KLs (KL A and KLB, respectively) were characterized by FTIR, 31P NMR, GPC and pHPZC analyses. The effects of biosorbent and adsorbate concentrations, pH, ionic strength, contact time and temperature on the MB adsorption were evaluated. The equilibrium, kinetic and thermodynamic parameters were calculated by Langmuir and Freundlich isotherms, pseudo-first and second order and Van't Hoff and Gibbs models, respectively. KL A and KL B presented peculiar structural features, mainly hydroxyls concentration and Mw values, which have influenced on the removal efficiency of MB and the adsorptive capacities of KL A (>80 %; ≥80 mg g-1) and KL B (>90 %; ≥20 mg g-1), respectively. The equilibrium, kinetic and thermodynamic parameters have shown that MB adsorption presented different mechanisms for each KL, but it only has driven by chemisorption for KL B. Therefore, KL A and KL B can be considered as potential novel biosorbents obtained through a clean, fast and simple route for textile wastewater treatment.

Development of an eco-friendly acetosolv protocol for tuning the acetylation of coconut shell lignin: Structural, antioxidant, solubility and UV-blocking properties.

The optimization of the parameters involved in lignin extraction is crucial for obtaining a lignin with specific structural features for its further valorization. The aim of this work was to develop an eco-friendly organosolv protocol for tuning the acetylation degree of coconut shell lignins (CSLs) by using MgCl2 and HCl as catalyst and co-catalyst, respectively. CSLs were obtained by mixing coconut shell powder with 90% v/v acetic acid combined to no catalyst, 2% v/v HCl and 2% w/v MgCl2 (1, 2 and 3 h) and 2% w/v MgCl2 combined to 0.1, 0.25 and 0.5% v/v HCl (2 h) at 110 °C. CSLs were characterized by FTIR, 1H NMR, GPC and TGA. The effects of the acetylation degree were evaluated on their antioxidant activity (DPPH assay) and UV-blocking capacity in sunscreen formulations. The results have shown that the use of HCl as co-catalyst increased the lignin yield (from 21.4 to 48.8%) and the acetylation degree (from 0.81 to 1.58 mmol g-1), which positively affected thermal (200 < Tonset < 226 °C), antioxidant (46.6 < IC50 < 67.5 µg mL-1) and UV-blocking capacities of CSLs. It can be concluded that the design of the organosolv process was capable of generating lignins with peculiar functionalities and properties through an eco-friendly protocol.

Elucidating the adsorption mechanism of Rhodamine B on mesoporous coconut coir-based biosorbents through a non-linear modeling and recycling approach.

The search for renewable adsorbent materials has increased continuously, being the agro-wastes an interesting alternative. This work aimed to elucidate the mechanism of adsorption of Rhodamine B on crude and modified coconut fibers from aqueous systems and the feasibility of reusing the biosorbents. The chemical modification of crude coconut fiber was carried out by the organosolv process. The biosorbents were characterized by lignocellulosic composition, FTIR, TGA, WCA, SEM, nitrogen adsorption/desorption (BET-BJH), and pH of zero point of charge (pHPZC) analyses. The batch adsorption tests evaluated the effects of the adsorbent and adsorbate dosages, contact time, and temperature on Rhodamine B adsorption. For elucidating the adsorption mechanisms involved in the process, the non-linear forms of kinetic and isotherm models were used. The regeneration of the biosorbents was evaluated by carrying out the desorption experiments. Modified coconut fiber had an increase in the amount of α-cellulose, which influenced its structural, morphological, surface, and porous properties. The removal efficiency of Rhodamine B was about 90% for modified coconut fiber and 36% for crude coconut fiber. The dye adsorption was spontaneous and endothermic for both biosorbents, showing higher spontaneity and affinity with the adsorbate for biosorbent modified. Therefore, the coconut fiber can be considered an alternative to the traditional adsorbent materials that allows the reuse by four times without performance loss, in which its adsorptive capacity has increased through its chemical modification by a biorefinery process.

Safety aspects of kraft lignin fractions: Discussions on the in chemico antioxidant activity and the induction of oxidative stress on a cell-based in vitro model.

Lignin is a complex phenolic biopolymer present in plant cell walls and a by-product of the cellulose pulping industry. Lignin has functional properties, such as antioxidant activity, that make it a potential natural active ingredient for health-care products. However, not all safety aspects of lignin fractions have been adequately investigated. Herein, we evaluated the antioxidant and genotoxic potential of two hardwood kraft lignins (F3 and F5). The chemical characterization of F3 and F5 demonstrated their thermal stability and the presence of different phenolic units, while the DPPH assay confirmed the antioxidant activity of these lignin fractions. Despite being antioxidants in the DPPH assay, F3 and F5 were capable of generating intracellular reactive oxygen species (ROS) and subsequently causing oxidative DNA damage (Comet assay) in HepG2 cells. The biological relevance of the DPPH assay might be uncertain in some cases; therefore, we suggest combining in chemico tests with biological system-based tests to determine efficacy and safety levels of lignins and define appropriate applications of lignins for consumer products. Moreover, kraft lignins obtained by acid precipitation may pose risks to human health; however, as genotoxicity is not the sole endpoint of toxicity required in hazard assessments, additional toxicological evaluations are needed.

Tailored organosolv banana peels lignins: Improved thermal, antioxidant and antimicrobial performances by controlling process parameters.

There is a growing environmental concern in the world for replacing the traditional petroleum-based products. The aim of this work was to evaluate the structure - property relationship of banana peel lignins (BPLs) as antioxidant and antimicrobial agents by controlling the parameters of organosolv process. The milled banana peel was hydrolyzed using an aqueous acetic acid solution (70, 80 and 90% v/v) and 2.0% v/v HCl at 110 °C for 1, 2 and 3 h. BPLs were characterized by FTIR, 1H NMR, 1H13C HSQC, 31P NMR, GPC and TGA. The antioxidant capacity of BPLs was evaluated by DPPH, ABTS and H2O2 assays, comparing their performance with that of ascorbic and gallic acid. The antimicrobial activity of BPLs was evaluated against E. coli. The reaction time and acetic acid/water ratio had significant effects on the yield and purity of BPLs. The composition of organosolv solution also affected their total amount of hydroxyls (0.71-0.82 mmol g-1), Mw (2759-3954 g mol-1), Tonset (232-254 °C), antioxidant and antimicrobial activities. It can be concluded that the control of organosolv parameters can be a useful tool for tuning the structural features of lignins and to maximize their performance.

Microwave-assisted selective acetylation of Kraft lignin: Acetic acid as a sustainable reactant for lignin valorization.

Lignin acetylation, one of the most widespread chemical modifications used for improve the solubility of this biopolymer in organic solvents and increase polymer-lignin compatibility, has been performed for decades using time-consuming methodologies and acetylating agents with serious drawbacks. Moreover, traditional acetylation reactions generally conduce to non-selective acetylation of both aliphatic and phenolic groups. In this work, we demonstrated that partial and selective acetylation of kraft lignin can be carried out through a greener, simple and fast microwave-assisted process using acetic acid as solvent and acetylating agent. Structural characterization via FTIR, 1H-13C HSQC and 31P NMR demonstrated that acetylation reaction occurs selectively only in aliphatic hydroxyls, preserving the phenolic hydroxyls. Optimal reaction conditions were obtained using 1% (v/v) of H2SO4 as catalyst and only 5 min as reaction time. The acetylated Kraft lignin (AKL) obtained, have enhanced solubility in organic solvents (ethyl acetate, chloroform and dichloromethane) compared to unmodified Kraft lignin (KL) and antioxidant capacity almost 8 times higher than a commercial antioxidant BHT. These characteristics make the partially and selectively acetylated Kraft lignin a potential green antioxidant additive to be used in polymers blends.

Enhanced microfibrillated cellulose-based film by controlling the hemicellulose content and MFC rheology.

Understanding of how hemicellulose acts on the rheology of microfibrillated cellulose in suspension or after drying is insufficient. In this study, different concentrations of hemicellulose in the cellulose pulp of Eucalyptus sp. were obtained by alkaline treatment with potassium hydroxide. The treated pulps and the suspension of microfibrils obtained were characterized by thermogravimetric analysis, zeta potential, scanning electron microscopy, rheological analysis, X-ray diffraction and dynamic mechanical analysis. The lowest hemicellulose content obtained was approximately 2% wt. Treatments with KOH above 10% did not cause a significant reduction in hemicellulose content and caused a change in the type of cellulose crystallinity. The rheological analysis showed that the apparent viscosity of the suspensions was strongly influenced by the presence of hemicellulose. The morphology of the MFC films of the treated pulps presented the appearance of voids with the reduction of hemicellulose content, generating a decrease in its mechanical properties.

Organic solvent fractionation of acetosolv palm oil lignin: The role of its structure on the antioxidant activity.

Pressed palm oil mesocarp fibers (PPOMF) are by-products from oil palm industry and represents a potential source of lignocellulosic biomass. In order to add value to this agro-waste, dewaxed palm oil acetosolv lignin (DPOAL) was extracted under eco-friendly pulping method. The chemical composition and structural characteristics of DPOAL were investigated. The results showed elevated yield (48.5%) and high purity (94.3%), besides a moderate average molecular weight (1394 g mol-1) and narrow polydispersity index (1.88). Structural characterization via FT-IR, 1H13C HSQC and 31P NMR indicated that DPOAL was a typical HGS-type lignin. In addition, to increase the phenolic hydroxyl contents and improve DPOAL's antioxidant properties through a simple method, a fractionation process with methanol, ethanol and acetone was carried out, obtaining the methanol (MeOH-F), ethanol (EtOH-F) and acetone (ACT-F) soluble fractions. These were characterized by FT-IR, DSC, 1H13C HSQC and 31P NMR, which showed higher values of phenolic and aliphatic hydroxyls groups compared to DPOAL. The antioxidant activity was evaluated by the free radical scavenging activity of 2,2­diphenyl­1­picrylhydrazyl radicals (DPPH·) and compared with commercial antioxidants, such as BHT and Irganox 1010. Interestingly, lignin samples had significantly lower IC50 values compared to commercial antioxidants, what suggests a great potential as novel natural antioxidant.

Poly(methyl methacrylate) films reinforced with coconut shell lignin fractions to enhance their UV-blocking, antioxidant and thermo-mechanical properties.

Lignin is a high added-value product obtained from agrowastes through organosolv process to yield materials for technological applications. Here, coconut shell organosolv lignin was fractionated using green solvents (acetone and ethanol) and incorporated in poly(methyl methacrylate) (PMMA) films. The non-fractionated (WCSAL) and soluble fractions (ACT-F and EtOH-F) were completely characterized regarding their structures. The fractionation process altered lignins molecular weights, decreasing with the increased solvent polarity, although the higher polarity favored the dissolution of acylated and methoxylated fragments. PMMA films incorporated with lignin fractions were analyzed by TGA and DSC, which showed improved thermal and thermo-oxidative stabilities. DMA analyses of the films indicated that lignin soluble fractions had a plasticizer effect, while non-fractionated lignin increased PMMA films glass transition temperature (Tg). The antioxidant capacity of the films was also enhanced with the addition of lignins, in which those incorporated with soluble fractions showed the lowest IC50 values. The optical properties and photo-stability were also considerably improved, especially in the UVA and UVB regions. Therefore, solvent-fractionation represents a potential sustainable process to obtain lignins featuring different chemical structures, which can be applied effectively in the enhancement of PMMA films properties.