Properties Of Lignin Research Articles

Isolation of β-O-4-Rich Lignin From Birch in High Yields Enabled by Continuous-Flow Supercritical Water Treatment.

The continuous flow supercritical water (scH2O) treatment of Birch wood (T=372-382 °C; t=0.3-0.7 s; p=260 bar) followed by alkali extraction of lignin allowed for the isolation of lignin and lignin carbohydrate complexes (LCCs) with a high number of β-O-4 moieties in the range 29-57/100 Ar (evaluated by quantitative 13C NMR analysis) in yields ranging between 13-19 wt % with respect to the initial wood. A "lightning rod effect" of carbohydrates has been claimed to explain the low degradation of β-O-4 bonds during the process. The structure of the isolated lignin was thoroughly elucidated via comprehensive NMR studies (HSQC, 13C and 31P). A low degree of condensation (DC)<5 % was found for all the lignin samples, which was only slightly dependent on the reaction severity. The number of aliphatic -OH, phenolic -OH, and -COOH groups was in the range 3.37-5.25, 1.41-2.31 and 0.39-0.73 mmol/g, respectively. The number of -COOH groups increased with increased severity, suggesting that oxidation can occur during the scH2O treatment. Furthermore, by simply varying the reaction severity, it was possible to tune important lignin properties, like the molar mass and the glass transition temperature (Tg).

Drying temperature effect on the characteristics of cationically polymerized kraft lignin

In this work, the effect of drying temperature (55–130 °C) on the properties of kraft lignin (KL) polymerized with [2-(methacryloyloxy)ethyl] trimethyl ammonium chloride, as a sustainable polymer (KLM) was investigated. KLM exhibited a 3-fold drop in charge density and a 10 % reduction in water solubility. These alterations were found to be associated with both chemical and physical changes determined by NMR and XPS analyses. At 55 °C, chain interactions were predominant due to electrostatic interactions amongst the pMETAC chains with the electronegative atoms present in KL. At 80, 105, and 130 °C drying temperatures, hydrolysis reactions predominated. The KLM polymer possessed, comparatively, a lesser resistance to thermal degradation than KL, and the KLM polymer had a more uniform thermal degradation behavior across the drying temperatures. Glass transition temperature, Tg, was shown to be comparable for KL across the various drying temperatures. KLM, however, showed an increasing trend as drying temperature increased, up to 130 °C, at which point Tg dropped due to KL degradation. Therefore, the drying temperature has a significant impact on the properties of kraft lignin and its cationic polymerized derivative, and it should be carefully selected to minimize the undesired changes in lignin properties.

Exploring the relationship between lignin structure and antioxidant property using lignin model compounds

Lignin has a natural polyphenol structure that is expected to replace chemically synthesized antioxidants as a native antioxidant with biodegradable and convenient source characteristics. However, the improvement of the antioxidant property of lignin and its application as an antioxidant are still somewhat limited due to the lack of understanding of the relationship between specific lignin structures and antioxidant property. Therefore, the study of the relationship between lignin structure and antioxidant property is crucial to realize the high-quality application of lignin. In this experiment, the scavenging ability of free 1,1-diphenyl-2-picrylhydrazyl (DPPH·) radicals was determined for different grades of acetylated tannins, typical lignin model compounds and different structural units of milled wood lignin to investigate the relationship between lignin structure and antioxidant property. Based on the experimental results, some structure-activity relationships were proposed and the mechanism of the antioxidant property of lignin was discussed. The number of phenolic hydroxyl groups was linearly and positively correlated with antioxidant property, and the scavenging of DPPH radicals increased significantly with the increase in the number of methoxy groups in the model compounds. Moreover, aldehyde and carboxyl groups had a negative effect on the antioxidant property of lignin, while methoxy, alkyl and alcohol hydroxyl groups played a positive role. The guaiacyl (G) and syringyl (S) units favored the antioxidant property, so the difference in the content of structural units in lignin under certain conditions of phenolic hydroxyl content also affected the antioxidant property. Therefore, the antioxidant property of aspen milled lignin was higher than that of other milled lignin from different wood species. Finally, the mechanism of DPPH free radical scavenging by lignin was revealed to better understand the relationship between lignin structure and antioxidant property.

Toward a green economy: Lignin-based hybrid materials as functional additives in flame-retardant polymer coatings

This study describes the combination of unique properties of lignin with TiO2 as an innovative and effective preparation method for high-performance flame-retardant additives that may be utilized as polymer coatings. The use of lignin resulted in numerous advantages including an increased number of functional groups, satisfactory biocompatibility, low toxicity, and high carbon content. The major benefit of lignin is associated with the reduced carbon footprint of the manufactured product. Lignin can be classified as a natural flame-retardant agent owing to the high amount of char formed during combustion. In turn, TiO2 exhibits high chemical stability and low operating costs and is considered a non-toxic and environmentally friendly material. During the experiments, commercial TiO2 in anatase crystallographic form, TiO2 synthesized from titanyl sulfate hydrate, and kraft lignin as well as organic–inorganic hybrid materials composed of these materials were evaluated as functional additives in epoxy-resin-based polymer coatings (Epidian 601) and their properties were investigated in detail. The cone colorimetry test confirmed that the obtained hybrids are effective flame-retardant additives for polymer coatings, with a notable fire hazard reduction observed for samples containing a synergistic system of titanium oxide and lignin. The coating with lignin was the most effective in fire suppression processes. The conducted thermal and mechanical investigations confirmed good performance properties of the coatings indicating thermal resistance up to 360 °C and Shore D hardness in a range of 80.36–86.28°Sh, accordingly. Optical profilometry investigations show that the lignin/TiO2 hybrids exhibit a stable topological surface shape as well as good dispersion and uniformity in the polymer matrix. All the conducted tests allowed confirmation that the presence of functional additives in polymer coatings in the form of lignin and TiO2 can be a promising alternative to non-biodegradable synthetic materials which improve flame-retardant properties.

Sustainable strategy for lignin etherification and its promotion of anti-UV aging PLA biocomposite

Achieving efficient modification of both phenolic (Phe)-OH and aliphatic (Aliph)-OH groups in lignin simultaneously via sustainable method, remained a significant challenge. In this study, a series of highly hydroxyl-substituted alkali lignin phenyl propylene ketone ethers (ALK) were obtained under 50 °C without any by-products via the mild and sustainable hydroxyl-yne click reaction method. Notably, phenolic (Phe)-OH content of lignin decreased from 4.12 mmol g−1 to 0.07 mmol g−1 with a conversion rate of 98 %, while the aliphatic (Aliph)-OH content of lignin decreased from 2.57 mmol g−1 to 0.10 mmol g−1 with a conversion rate of 96 %. Owing to the efficient etherification, ALK showed excellent organic solvent (such as trichloromethane, DCM, THF, and acetone) solubility, which thereby improving the interfacial compatibility between ALK and PLA matrix. 3 wt% ALK obviously enhanced the mechanical properties of ALK/PLA biocomposite films, with the yield strength, breaking strength, and Young’s modulus improving by 114.2 %, 30.7 % and 250.2 %, respectively. Additionally, due to the newly introduced vinyl ether bonds (−C–O–CC–) in ALK by hydroxyl-yne click reaction, only 1 % ALK could endow ALK/PLA biocomposite with excellent UV shielding (100 %), high transmittance (84.3 %) and Anti-UV aging property. The yield strength and Young’s modulus represented an increase of 209 % and 86 %, respectively, even after 3 h of UV-irradiation. This study presents an environmentally friendly lignin functionalization method that unleashes the inherent Anti-UV aging properties of lignin, opening new avenues for the development of high-performance lignin-based composites.

Influence of Oxygen Exposure on Lignin Preservation during Sediment Lateral Transport in the Ocean: Insights from Molecular Dynamics Simulations.

Understanding the fate of terrestrial organic carbon (terrOC) preservation in the marine environments is critical for deciphering the biogeochemical processes associated with the global carbon cycle and the Earth's climate change. The mechanisms controlling terrOC preservation are not completely understood, while lateral oxygen exposure time (OET) is considered as a critical controlling factor. Here, we first utilized molecular dynamics simulations to investigate the structural properties of lignin under anoxic, suboxic, and oxic conditions for understanding the mechanisms of terrOC preservation during sediment lateral transport in the ocean. Our finding suggested that oxygen exposure was indispensable for terrOC degradation through influencing the structural stability and reactivity of lignin. Our simulated results showed that in suboxic environments, prolonged OET may enhance terrOC preservation. Our organic geochemical results suggested that terrOC preferably preserved in coarse silts (20-63 μm) than fine silts (<20 μm) in suboxic environments, largely due to hydrodynamics-driven prolonged OET in coarse sediments, which may efficiently reduce CO2 emissions. Overall, our study sheds new light on the mechanisms of lateral OETs on terrOC preservation in suboxic conditions and, from a unique molecular structural perspective, provides insights into the impact of prolonged OETs on terrOC oxidative degradation in the marine environment.

Carbonisation of lignin in the presence of a eutectic salt mixture: Identifying the lignin properties that govern the characteristics of the resulting carbon material

Numerous studies have explored the behaviour of various lignin types during carbonisation. Yet, misconceptions persist regarding the effects arising from both the source plant and production method of lignin. Lignin is often referenced merely by type, lacking detailed characterisation. Our research examines the properties of three lignin types, elucidates their behaviour during pyrolysis, and establishes the structure-property correlation and interaction of lignin with deep eutectic solvents. By combining several analytical techniques — including NMR, FTIR, XPS, TGA-MS for functional group detection, and HPLC, EA, and ICP for compositional analysis, alongside particle size distribution and SEC for morphology — we can conduct a thorough analysis that facilitates a meaningful comparison across lignin types. This approach allows for better control over the desired carbon properties. Furthermore, we demonstrate how modification with deep eutectic solvents enables the production of biochar from different lignin types, exhibiting properties conducive to large-scale, one-step sustainable production of biochar.

Design of a hybrid nanoscaled skin photoprotector by boosting the antioxidant properties of food waste-derived lignin through molecular combination with TiO2 nanoparticles

TiO2 nanoparticles loaded with pistachio shell lignin (8 % and 29 % w/w) were prepared by a hydrothermal wet chemistry approach. The efficient interaction at the molecular level of the biomacromolecule and inorganic component was demonstrated by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–Visible (UV–Vis), Fourier transform infrared (FT-IR), dynamic light scattering (DLS), and electron paramagnetic resonance (EPR) analysis. The synergistic combination of lignin and TiO2 nanoparticles played a key role in the functional properties of the hybrid material, which exhibited boosted features compared to the separate organic and inorganic phase. In particular, the hybrid TiO2-lignin nanoparticles showed a broader UV–Vis protection range and remarkable antioxidant performance in aqueous media. They could also better protect human skin explants from the DNA damaging effect of UV radiations compared to TiO2 as indicated by lower levels of p-H2A.X, a marker of DNA damage, at 6 h from exposure. In addition, the samples could protect the skin against the structural damage occurring 24 h post UV radiations by preventing the loss of keratin 10. These results open new perspectives in the exploitation of food-waste derived phenolic polymers for the design of efficient antioxidant materials for skin photoprotection in a circular economy perspective.

Insights into the Chemical Structure and Antioxidant Activity of Lignin Extracted from Bamboo by Acidic Deep Eutectic Solvents.

Deep eutectic solvents (DESs) composed of choline chloride as hydrogen bond acceptors (HBAs) and six organic acids as hydrogen bond donors (HBDs) were used to extract lignin from bamboo (Phyllostachys edulis (Carrière) J. Houz.). The structures of the DES-extracted lignin samples were analyzed by Fourier-transform infrared spectroscopy (FT-IR), UV-visible spectroscopy (UV-vis), thermogravimetric analysis (TG), and gel permeation chromatography (GPC) to investigate the relationship between the chemical structure of lignin and its antioxidant activity. The results showed that DES treatment removed a large portion of the lignin (73.37-86.38%) from bamboo, and the chemical structure of lignin was changed due to the use of different types of HBDs. The extracted lignin exhibited good UV-vis light shielding properties, thermal stability, and antioxidant activity. Moreover, the total phenolic hydroxyl content of lignins was positively correlated with their antioxidant activity, while the molecular weight of lignins was negatively correlated with their antioxidant activity. Notably, lignin extracted with choline chloride-p-toluenesulfonic acid had the highest phenolic hydroxyl content and lower molecular weight, showing the strongest antioxidant activity (IC50DPPH = 417.69 μg/mL, IC50ABTS = 58.62 μg/mL). This study confirms the high thermal stability, excellent antioxidant activity, and UV shielding properties of lignin extracted with choline chloride-organic acid DESs, suggesting its potential application in the fields of antioxidants and material modifiers.

Modified lignin by deep eutectic solvent as a novel coupling agent for wood-plastic composites

In this work, the influence of modified lignin by Deep Eutectic Solvent (DES) as a novel bio coupling agent on the various properties of wood flour- polypropylene composites (WPCs) was investigated. For this purpose, extracted lignin from Bagasse Soda black liquor was modified with Choline chloride–ZnCl2 deep-eutectic solvent (ChCl–ZnCl2 DES) and then different ratios of unmodified and modified lignin (0, 1, 3 and 5 wt%) were added to the wood flour/polypropylene mixture. Different properties of lignin after modification by DES along with physical and mechanical properties of the manufactured composites were measured according to the relevant standard methods. The FTIR analysis indicated that DES- modified lignin has a higher proportion of phenolic hydroxyl groups (1213 cm−1) and a lower one of methoxy groups (2854 cm−1) when compared to virgin lignin. DSC analysis also showed that the glass transition temperature (Tg) of lignin decreased from 90 °C to 80 °C by DES treatment. Based on the results obtained, the physical and mechanical properties of WPCs were continuously improved by increasing the modified lignin content from 1 to 5 wt%. The composites with DES-treated lignin presented lower water absorption and thickness swelling as well as higher flexural, tensile and impact properties compared to those prepared with unmodified lignin at the same fixed level of lignin. Moreover, based on the finding of this research, the composites with 5 wt% DES-treated lignin have relatively better physical and mechanical properties than those made from 2 wt% maleic anhydride polypropylene (MAPP) as a control sample. Modification of lignin with DES improves its uniform dispersion in the polymer matrix according to Scanning Electron Microscopy (SEM) images.

Synthesis and Antibacterial Properties of Novel Quaternary Ammonium Lignins.

The ongoing demand for effective antimicrobial materials persists, and lignin emerges as a promising natural antibacterial material with renewable properties. The adaptability of lignin to various chemical modifications offers avenues to enhance its antimicrobial activity. Here, we employed chloromethylation and subsequent functionalization with variable tertiary N-alkyl dimethyl amines to produce C6-C18 quaternary ammonium lignins (QALs) from hardwood (aspen), softwood (pine), and grass (barley straw). Successful synthesis of QALs was confirmed through NMR and FTIR analysis results along with an increase in the surface ζ-potential. Antibacterial activity of QALs against clinical strains of Klebsiella pneumoniae and methicillin-resistant Staphylococcus aureus was assessed using minimal bactericidal concentration (MBC) assay and agar growth inhibition zone (ZOI) test. The antibacterial activity of QALs was found to be higher than that of the unmodified lignins. QALs with longer alkyl chains demonstrated an MBC of 0.012 mg/L against K. pneumoniae already after 1 h of exposure with similar effect size reached after 24 h for S. aureus. For all the lignins, an increase in alkyl chain length resulted in an increase in their bactericidal activity. MBC values of C14-C18 QALs were consistently lower than the MBC values of QALs with shorter alkyl chains. Besides the alkyl chain length, MBC values of barley and pine QALs were negatively correlated with the surface ζ-potential. While alkyl chain length was one of the key properties affecting the MBC values in a liquid-based test, the agar-based ZOI test demonstrated an antibacterial optimum of QALs at C12-C14, likely due to limited diffusion of QALs with longer alkyl chains in a semisolid medium.

Capability lignin from Acacia crassicarpa black liquor as an environmentally benign antibacterial agent to produce antibacterial and hydrophobic textiles

Recently, the growing health awareness of society on the utilization of fabrics has led to an increasing demand for natural-based antibacterial textiles. Lignin, a generous polyphenol compound in nature, is capable of preventing bacterial growth; in particular, it dwells bacteria closely together on human skin, such as Staphylococcus epidermidis, Bacillus subtilis, Propionibacterium acnes, and Staphylococcus aureus. However, the antibacterial properties of lignin are limited by factors such as the lignin concentration, source, and type of bacteria. This study aimed to evaluate the potency of lignin as an antibacterial agent for textiles. Moreover, the thermal properties and wettability of the textile after lignin coating were also investigated. This study showed that lignin isolation methods significantly contributed to the inhibition of bacterial growth in the clear zone diameter. In addition, the lignin structure, lignin concentration, and type of bacteria had notably different antibacterial effects. SEM images showed that lignin was successfully coated on the fiber, and the antibacterial textile was successfully fabricated with clear zones in the range of 0.1–0.5 cm against four different bacteria. Lignin did not significantly improve the thermal stability of the textile, as proven by the TGA results. After the HDTMS coating by dispersion method, the wettability of the lignin-textile improved to that of the hydrophobic material, with a contact angle greater than 119.05° with excellent antibacterial properties (clear zone of 0.1–0.43 cm).

The Enhancement Origin of Antioxidant Property of Carboxylated Lignin Isolated from Herbaceous Biomass Using the Maleic Acid Hydrotropic Fractionation.

Lignin is endowed with antioxidant activity due to its diverse chemical structure. It is necessary to explore the relationship between antioxidant activity and the chemical structure of the lignin to develop its high-value utilization. Herein, we employed maleic acid (MA) as a hydrotropic agent to preferably isolate the lignin from distinct herbaceous sources (wheat straw and switchgrass) under atmospheric pressure conditions. The resultant acid hydrotropic lignin (AHL) isolated from wheat straw exhibited high radical scavenging rates, up to 98% toward DPPH and 94% toward ABTS. Further investigations indicated that during the MA hydrotropic fractionation (MAHF) process, lignin was carboxylated by MA at γ-OH of the side-chain, providing additional antioxidant activity from the carboxy group. It was also found that the radical scavenging rate of AHL has a positive correlation with carboxyl, phenolic hydroxyl contents, and the S-G (syringyl-guaiacyl) ratio, which could be realized by increasing the MAHF severity. Overall, this work underlies the enhancement origin of the antioxidant property of lignin, which will facilitate its application in biological fields as an efficient, cheap, and renewable antioxidant additive.

The Role of Lignin Molecular Weight on Activated Carbon Pore Structure.

Over the past decade, the production of biofuels from lignocellulosic biomass has steadily increased to offset the use of fuels from petroleum. To make biofuels cost-competitive, however, it is necessary to add value to the "ligno-" components (up to 30% by mass) of the biomass. The properties of lignin, in terms of molecular weight (MW), chemical functionality, and mineral impurities often vary from biomass source and biorefinery process, resulting in a challenging precursor for product development. Activated carbon (AC) is a feasible target for the lignin-rich byproduct streams because it can be made from nearly any biomass, and it has a market capacity large enough to use much of the lignin generated from the biorefineries. However, it is not known how the variability in the lignin affects the key properties of AC, because, until now, they could not be well controlled. In this work, various fractions of ultraclean (<0.6% ash) lignin are created with refined MW distributions using Aqueous Lignin Purification using Hot Agents (ALPHA) and used as precursors for AC. AC is synthesized via zinc chloride activation and characterized for pore structure and adsorption capacity. We show that AC surface area and the adsorption capacity increase when using lignin with increasing MW, and, furthermore, that reducing the mineral content of lignin can significantly enhance the AC properties. The surface area of the AC from the highest MW lignin can reach ~1830 m2/g (absorption capacity). Furthermore, single step activation carbonization using zinc chloride allows for minimal carbon burn off (<30%), capturing most of the lignin carbon compared to traditional burn off methods in biorefineries for heat generation.

Lignin-based vitrimer containing dynamic borate ester bonds with intrinsic photoconversion and excellent photothermal remoldability

The development of photoresponsive shape memory materials based on the photothermal conversion properties of lignin and the low activation energy of the dynamic covalent borate bond is of great importance. In this paper, a kind of lignin-based vitrimer polymer (LBP) containing dynamic boronic ester bonds was prepared by a “sulfhydryl-epoxy” click reaction and etherification reaction. The results show that the rigid segment EP-EL (lignin-based epoxy resin) and BDB (2,2′-(1,4-phenylene)-bis-[4-mercapto-1,3,2-dioxaneborane]) with benzene ring structure can impart tensile strength (20.8 MPa) to the LBP, while the flexible segment PEG imparts good elongation at break (15 %). The dynamic binding and dissociation exchange mechanism of the boronic ester bonds enables LBP to exhibit thermal remodelling properties (up to 36.2 %) and water-assisted self-healing properties at room temperature (up to 49.0 %). In addition, LBP exhibits excellent thermal and light-responsive shape memory properties due to its own photothermal conversion performance (photothermal conversion efficiency up to 18.2 %) and the dynamic boronic ester bond thermal activation bond exchange mechanism. The insulating properties of LBP make it suitable for use in high temperature protection circuit devices and light-responsive circuit devices. This study provides new insights into the design and application of Vitrimer and photoresponsive shape memory polymers, and also offers a new avenue for high-value utilization of lignin.

Decolorization of Lignin for High-Resolution 3D Printing of High Lignin-Content Composites.

Lignin, one of the most abundant biomaterials and a large-scale industrial waste product, is a promising filler for polymers as it reduces the amount of fossil resources and is readily available. 3D printing is well-known for producing detailed polymer structures in small sizes at low waste production. Especially light-assisted 3D printing is a powerful technique for production of high-resolution structures. However, lignin acts as a very efficient absorber for UV and visible light limiting the printability of lignin composites, reducing its potential as a high-volume filler. In this work, the decolorization of lignin is presented for high-resolution 3D printing of biocomposites with lignin content up to 40wt.%. Organosolv lignin (OSL) is decolorized by an optimized low-energy process of acetylation and subsequent UV irradiation reducing the UV absorbance by 71%. By integration of decolorized lignin into bio-based tetrahydrofurfuryl acrylate (THFA), a lignin content of 40wt.% and a resolution of 250µm is achieved. Due to the reinforcing properties of lignin, the stiffness and strength of the material is increased by factors of 15 and 2.3, respectively. This work paves the way for the re-use of a large amount of lignin waste for 3D printing of tough materials at high resolution.

One pot green process for facile fractionation of sorghum biomass to lignin, cellulose and hemicellulose nanoparticles using deep eutectic solvent

Complete valorization of lignocellulosic biomass is crucial for bio-based biorefineries to fulfil the circular bioeconomy concept. However, the existence of lignin carbohydrate complexes (LCC) in biomass hinders the simultaneous fractionation of biomass components, such as lignin, hemicellulose and cellulose, for subsequent biorefining processes. This study explores for the first time a novel approach tailored for the deconstruction of sorghum biomass components through efficient breakdown of LCC. Selective targeting of the major LCC linkages binding xylan and lignin was performed using an ultrasound-assisted deep eutectic solvent under mild treatment conditions. This process yielded a maximum cellulose content of 98.3 %, hemicellulose content of 95.2 %, and lignin content of 94.6 %, with the highest purities of 99.43 %, 96.71 %, and 98.12 %, respectively. FTIR, 2D-HSQC NMR and XRD analyses confirmed that most of the structural properties of lignin, hemicellulose, cellulose are retained. The lignocellulosic components were successfully valorised to cellulose, hemicellulose, and lignin nanoparticles with mean sizes of 64.5 ± 6 nm, 72.8 ± 4 nm and 57.2 ± 8 nm respectively, with good thermal stability. The proposed green process enables the complete utilization of agro-residue feedstock for the preparation of biomass-derived nanoparticles, thereby accelerating the economic and industrial prospects of bio-based biorefineries.

The Antimicrobial Properties of Technical Lignins and Their Derivatives-A Review.

Lignin represents one of the most abundant plant-derived polymers. It is mostly present in the cell wall, and its primary role is to provide mechanical support to the plant. Chemical processes during wood-pulping yield diverse technical lignins with distinct characteristics. Due to their complex and variable nature, technical lignins are often undervalued and are mainly used as burning fuel in mills. However, various technical lignins have been shown to possess antimicrobial properties. Consequently, there is an increasing interest in understanding the properties and conditions that underlie their antimicrobial characteristics and how we can utilize them for practical applications. This review, for the first time, comprehensively summarized the antimicrobial activities of technical lignins and their potential antimicrobial applications.

ENHANCEMENT OF PHENOLIC CONTENT AND ANTIOXIDANT PROPERTIES THROUGH CHEMICAL AND BIOCHEMICAL REATMENT OF LIGNIN-RICH RICE STRAW RESIDUE

Valorization of lignin in biorefineries is important as this can lead to enhancement of chemical and physical properties of lignin, making it suitable for applications in polymers, composites and adhesives. Lignin valorization requires overcoming recalcitrance and tailoring for different uses. Here, lignin was extracted from rice straw lignin-rich residue at pH 12, using 4% magnesium oxide and 6% sodium hydroxide on a dry w/w basis. The extracted lignin-rich stream, which had a pH in the range of 9-10, was used further for biochemical transformation. Towards that end, Pseudomonas putida, Sphingomonas paucimobilis, Pseudomonas fluorescens and Bacillus tequilensis were screened for their capability of aromatic dye decolourization. The results of the study show an increase in the total phenolic content in lignin between 50% and 55% after 144 h of treatment with Pseudomonas putida. Concomitant with the increase of phenolics, a four-fold increase in antioxidant activity in gallic acid equivalents was also observed when Pseudomonas putida was used.

In Ukrainian

An important environmental problem is the removal of contaminants and the purification of domestic and industrial water from pollutants of various nature. There is a separate issue of cleaning the effluents of pharmaceutical enterprises. Various chemical and physical methods are used to solve these problems, such as settling, coagulation, filtration, and sorption techniques. Adsorption with using efficient and reusable adsorbents is the most effective and cheap. In recent years special attention has been paid to the use of sorption materials based on hydrolysis lignin, which has a high sorption activity in relation to ions of some heavy metals, dyes, organic compounds and pharmaceuticals. The use of lignin as an adsorbent simultaneously solves two problems: the disposal of paper production waste and the purification of sewage from various types of pollutants. The aim of this work was to study the sorption properties of hydroylysis lignin in aqueous solution in relation to some medical substances of different chemical nature, existing in solution in cationic, anionic or neutral forms. The point of zero charge of hydrolysis lignin was determined, which is equal to рНPZC = 4.95. The adsorption of rivanol, proflavin, doxorubicin, levofloxacin, furacilin, and salicylic acid by hydrolysis lignin was studied as dependence on the pH of the solutions and the concentration of adsorbates. It was found that adsorption largely depends on the structure of the pharmaceuticals and the pH values of the solutions. It is shown that the studied medical compounds, which exist in the solution in the form of cations, are adsorbed the best (rivanol, proflavin, doxorubicin). Adsorption of these substances occurs mainly due to electrostatic interaction with negatively charged surface groups. Adsorption of anionic form (salicylic acid) is the smallest and is observed only at quite low pH values. Levofloxacin is adsorbed mainly in the form of zwitter ions, and furacilin is in neutral form. The adsorption of these both compounds occupies an intermediate value of adsorption amount. The obtained adsorption isotherms are well lined up in Langmuir coordinates. Quantitative parameters of adsorption values - of maximum adsorption and equilibrium constants were calculated. Quite high values of these parameters indicate that hydrolysis lignin can be used as an adsorbent for the removal of these pharmaceuticals.