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Arabinogalactan (AG), extracted from larch wood, is a β-1,3-galactan backbone and β-1,6-galactan side chains with attached α-1-arabinofuranosyl and β-1-arabinopyranosyl residues. Although the structural characteristics of arabinogalactan II type have already been studied, its functionalization using 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) oxidation remains a promising avenue. In this study, the oxidation of AG, a neutral polysaccharide, was carried out using the TEMPO/NaBr/NaOCl system, resulting in polyuronides with improved functional properties. The oxidation of AG was controlled by analyzing portions of the reaction mixture using spectrophotometric and titration methods. To determine the effect of the TEMPO/NaBr/NaOCl system, air-dried samples of native and oxidized AG were studied by Fourier-transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy, as well as by gel permeation chromatography. Compounds that model free (1,1-diphenyl-2-picrylhydrazyl (DPPH)) and hydroxyl radicals (iron(II) sulfate, hydrogen peroxide, and salicylic acid) were used to study the antioxidant properties. It was found that, in oxidized forms of AG, the content of carboxyl groups increases by 0.61 mmol compared to native AG. The transformation of oxidized AG into the H+ form using a strong acid cation exchanger leads to an increase in the number of active carboxyl groups to 0.76 mmol. Using FTIR spectroscopy, characteristic absorption bands (1742, 1639, and 1403 cm−1) were established, indicating the occurrence of oxidative processes with a subsequent reduction in the carboxyl group. The functionality of AG was also confirmed by gel permeation chromatography (GPC), which is reflected in an increase in molecular weights (up to 15,700 g/mol). A study of the antioxidant properties of the oxidized and protonated forms of AG show that the obtained antioxidant activity (AOA) values are generally characteristic of polyuronic acids. Therefore, the TEMPO oxidation of AG and other neutral polysaccharides can be considered a promising approach for obtaining compounds with the necessary controlled characteristics.

The relevance of the study is determined by the search for new solid fuels to expand the fuel and energy complex and improve resource-saving and environmentally friendly energy. The main aim: a comprehensive study of cardboard and coal combustion, including the determination of the main characteristics of the combustion of solid fuel mixtures, the determination of the main kinetic parameters and the establishment of the role of the components in the mixture combustion. Object: solid fuel mixture based on Kaa-Khem coal and cardboard. Methods. Thermal characteristics of fuels are determined according to: analytical moisture – SS R 33503-2015; ash content – SS R 55661-2013; yield of volatile components – SS R 55660-2013; calorific value – SS R 147-2013; content of carbon, hydrogen, nitrogen – SS R 32979-2014; oxygen – SS R 27313-2015; sulfur – SS 8606-2015. The fuel combustion was studied using an SDT Q600 differential thermal analyzer (TA Instruments-Waters LLC, USA). Ignition and burnout temperatures were determined using the curve crossing method. To determine the kinetic characteristics of individual fuels and fuel mixtures, a method based on the Coates–Redfern model was used. Results. The heat of combustion of Kaa-Khem coal is twice that of cardboard, while the volatile content of cardboard is 1,8 times higher than that of coal, which makes cardboard a promising additional fuel. An increase in the mass fraction of cardboard in the mixture does not affect the ignition temperature of the mixture and is about 300 °С. The addition of 25 % cardboard to coal has a positive effect on coal carbon residue combustion, increasing the maximum reaction rate by 30 % compared to the calculated data. The activation energy in this case is reduced by 3 9%, the combustion index is reduced by 2,5 times. The results of this study can be applied in the design of new heat and power equipment, or be taken into account when converting coal-burning boilers to burning solid fuel mixtures.

A new method for extractive-catalytic fractionation of aspen wood to produce microcrystalline (MCC), microfibrillated (MFC), nanofibrilllated (NFC) celluloses, xylan, and ethanollignin is suggested in order to utilize all of the main components of wood biomass. Xylan is obtained with a yield of 10.2 wt.% via aqueous alkali extraction at room temperature. Ethanollignin was obtained with a yield of 11.2 wt.% via extraction with 60% ethanol from the xylan-free wood at 190 °C. The lignocellulose residue formed after the extraction of xylan and ethanollignin was subjected to catalytic peroxide delignification in the acetic acid-water medium at 100 °C in order to obtain microcrystalline cellulose. MCC is hydrolyzed with 56% sulfuric acid and treated with ultrasound to produce microfibrillated cellulose and nanofibrillated cellulose. The yields of MFC and NFC were 14.4 and 19.0 wt.%, respectively. The average hydrodynamic diameter of NFC particles was 36.6 nm, the crystallinity index was 0.86, and the average zeta-potential was 41.5 mV. The composition and structure of xylan, ethanollignin, cellulose product, MCC, MFC, and NFC obtained from aspen wood were characterized using elemental and chemical analysis, Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) analyses, Gas chromatography (GC), Gel permeation-chromatography (GPC), Scanning electron microscopy (SEM), Atomic force microscopy (AFM), Dynamic light scattering (DLS), Thermal gravimetric analysis (TGA).

To ensure the high quality of water, it is necessary to remove toxic pollutants. At present, purification of water is implemented using various sorbents. The efficient sorption materials are modified polysaccharides. In this study, we report on a new environmentally friendly method for modifying larch hemicellulose—arabinogalactan (AG)—with polybasic carboxylic acids (citric, succinic, oxalic, and adipic) to obtain composite materials. The synthesized AG derivatives have been explored by a complex of physicochemical methods, including gel permeation chromatography (GPC), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffractometry (XRD), scanning electron microscopy (SEM), and sorption capacity investigations. It is shown that the heat treatment results in the formation of additional inter- and intramolecular bonds between carboxylic acids and polysaccharide molecules. The formation of ester bonds has been confirmed by the appearance of absorption bands in the IR spectra in the range of 1750–1690 cm−1. It has been found, using the TGA study, that the most thermally stable (up to 190 °C) sample is arabinogalactan oxalate obtained under heat treatment. The SEM study of the synthesized AG films has shown that the modified samples have the homogeneous film surface ensured by cross-linking. It has been established, when studying the sorption properties of the AG derivatives, that AG succinate (82.52%) obtained by lyophilization has the highest sorption capacity, due to the developed mesoporous surface, which, in turn, makes the synthesized films promising eco-friendly materials for use as drug carriers, sorbents, and water treatment agents.

Cellulose sulfates are important biologically active substances with a wide range of useful properties. The development of new methods for the production of cellulose sulfates is an urgent task. In this work, we investigated ion-exchange resins as catalysts for the sulfation of cellulose with sulfamic acid. It has been shown that water-insoluble sulfated reaction products are formed in high yield in the presence of anion exchangers, while water-soluble products are formed in the presence of cation exchangers. The most effective catalyst is Amberlite IR 120. According to gel permeation chromatography, it was shown that the samples sulfated in the presence of the catalysts KU-2-8, Purolit s390 plus, and AN-31 SO42− underwent the greatest degradation. The molecular weight destribution profiles of these samples are noticeably shifted to the left towards low-molecular-weight compounds with an increase in fractions in the regions Mw ~2.100 g/mol and ~3.500 g/mol, indicating the growth of microcrystalline cellulose depolymerization products. The introduction of a sulfate group into the cellulose molecule is confirmed using FTIR spectroscopy by the appearance of absorption bands at 1245–1252 cm−1 and 800–809 cm−1, which correspond to the vibrations of the sulfate group. According to X-ray diffraction data, amorphization of the crystalline structure of cellulose is observed during sulfation. Thermal analysis has shown that with an increase in the content of sulfate groups in cellulose derivatives, thermal stability decreases.

We report on the kinetics of pyrolysis of bark wood of four coniferous tree species: fir (Abies sibirica), larch (Larix sibirica), spruce (Picea obovata), and cedar (Pinus sibirica) denoted as FB, LB, SB, and CB, respectively. Thermogravimetry (TG) and differential scanning calorimetry (DSC) methods were used to study the influence of KCl and K3PO4 compounds on the process of thermal decomposition of fir bark and determine the main thermal effects accompanying this process. As a result of the studies carried out, it was found that KCl additives practically do not affect the decomposition of hemicelluloses, but they shift the maximum decomposition of the cellulose peak in the direction of decreasing temperature to 340.9 °C compared to untreated bark (357.5 °C). K3PO4 promotes the simultaneous decomposition of hemicelluloses and cellulose in the temperature range with a maximum of 277.8 °C. In both cases, the additions of KCl and K3PO4 reduce the maximum rate of weight loss, which leads to a higher yield of carbon residues: the yield of char from the original fir bark is 28.2%, in the presence of K3PO4 and KCl it is 52.6 and 65.0%, respectively. Using the thermogravimetric analysis in the inert atmosphere, the reaction mechanism has been established within the Criado model. It is shown that the LB, SB, and CB thermal decomposition can be described by a two-dimensional diffusion reaction (D2) in a wide range (up to 0.5) of conversion values followed by the reactions with orders of three (R3). The thermal decomposition of the FB occurs somewhat differently. The diffusion mechanism (D2) of the FB thermal decomposition continues until a conversion value of 0.6. As the temperature increases, the degradation of the FB sample tends to R3. It has been found by the thermogravimetric analysis that the higher cellulose content prevents the degradation of wood. The bark wood pyrolysis activation energy has been calculated within the Coats–Redfern and Arrhenius models. The activation energies obtained within these models agree well and can be used to understand the complexity of biomass decomposition.

A new approach is being considered for obtaining microfibrillated cellulose with a low degree of polymerization by sulfuric acid hydrolysis with simultaneous ultrasonic treatment under mild conditions (temperature 25 °C, 80% power control). Samples of initial cellulose, MCC, and MFC were characterized by FTIR, XRF, SEM, DLS, and TGA. It was found that a high yield of MFC (86.4 wt.%) and a low SP (94) are observed during hydrolysis with ultrasonic treatment for 90 min. It was shown that the resulting microfibrillated cellulose retains the structure of cellulose I and has an IC of 0.74. It was found that MFC particles are a network of fibrils with an average size of 91.2 nm. ζ-potential of an aqueous suspension of MFC equal to −23.3 mV indicates its high stability. It is noted that MFC has high thermal stability, the maximum decomposition temperature is 333.9 °C. Simultaneous hydrolysis process with ultrasonic treatment to isolate MFC from cellulose obtained by oxidative delignification of spruce wood allows to reduce the number of stages, reduce energy costs, and expand the scope.

Noble metal-based catalysts are widely used to intensify the processes of reductive fractionation of lignocellulose biomass. In the present investigation, we proposed for the first time using the inexpensive NiCuMo/SiO2 catalyst to replace Ru-, Pt-, and Pd-containing catalysts in the process of reductive fractionation of abies wood into bioliquids and cellulose products. The optimal conditions of abies wood hydrogenation were selected to provide the effective depolymerization of wood lignin (250 °C, 3 h, initial H2 pressure 4 MPa). The composition and structure of the liquid and solid products of wood hydrogenation were established. The NiCuMo/SiO2 catalyst increases the yield of bioliquids (from 36 to 42 wt%) and the content of alkyl derivatives of methoxyphenols, predominantly 4-propylguaiacol and 4-propanolguaiacol. A decrease in the molecular mass and polydispersity (from 1870 and 3.01 to 1370 Da and 2.66, respectively) of the liquid products and a threefold increase (from 9.7 to 36.8 wt%) in the contents of monomer and dimer phenol compounds were observed in the presence of the catalyst. The solid product of catalytic hydrogenation of abies wood contains up to 73.2 wt% of cellulose. The composition and structure of the solid product were established using IRS, XRD, elemental and chemical analysis. The data obtained show that the catalyst NiCuMo/SiO2 can successfully replace noble metal catalysts in the process of abies wood reductive fractionation into bioliquids and cellulose.

The physicochemical properties of binary systems are of great importance for the application of the latter. We report on the investigation of an ammonium sulfamate–urea binary system with different component ratios using a combination of experimental (FTIR, XRD, TGA/DSC, and melting point) and theoretical (DFT, QTAIM, ELF, RDG, ADMP, etc.) techniques. It is shown that, at a temperature of 100 °C, the system under study remains thermally and chemically stable for up to 30 min. It was established using X-ray diffraction analysis that the heating time barely affects the X-ray characteristics of the system. Data on the aggregate states in specified temperature ranges were obtained with thermal analysis and determination of the melting point. The structures of the ammonium sulfamate–urea system with different component ratios were optimized within the density functional theory. The atom-centered density matrix propagation calculation of the ammonium sulfamate–urea system with different component ratios was performed at temperatures of 100, 300, and 500 K. Regardless of the component ratio, a regular increase in the potential energy variation (curve amplitude) with an increase in temperature from 100 to 500 K was found.

For the first time, the process of birch ethanol lignin sulfation with a sulfamic acid-urea mixture in a 1,4-dioxane medium was optimized experimentally and numerically. The high yield of the sulfated ethanol lignin (more than 96%) and containing 7.1 and 7.9 wt % of sulfur was produced at process temperatures of 80 and 90 °C for 3 h. The sample with the highest sulfur content (8.1 wt %) was obtained at a temperature of 100 °C for 2 h. The structure and molecular weight distribution of the sulfated birch ethanol lignin was established by FTIR, 2D 1H and 13C NMR spectroscopy, and gel permeation chromatography. The introduction of sulfate groups into the lignin structure was confirmed by FTIR by the appearance of absorption bands characteristic of the vibrations of sulfate group bonds. According to 2D NMR spectroscopy data, both the alcohol and phenolic hydroxyl groups of the ethanol lignin were subjected to sulfation. The sulfated birch ethanol lignin with a weight average molecular weight of 7.6 kDa and a polydispersity index of 1.81 was obtained under the optimum process conditions. Differences in the structure of the phenylpropane units of birch ethanol lignin (syringyl-type predominates) and abies ethanol lignin (guaiacyl-type predominates) was manifested in the fact that the sulfation of the former proceeds more completely at moderate temperatures than the latter. In contrast to sulfated abies ethanol lignin, the sulfated birch ethanol lignin had a bimodal and wider molecular weight distribution, as well as less thermal stability. The introduction of sulfate groups into ethanol lignin reduced its thermal stability.

Soda lignin is a by-product of the soda process for producing cellulose from grassy raw materials. Since a method for the industrial processing of lignin of this type is still lacking, several research teams have been working on solving this problem. We first propose a modification of soda lignin with sulfamic acid over solid catalysts. As solid catalysts for lignin sulfation, modified carbon catalysts (with acid sites) and titanium and aluminum oxides have been used. In the elemental analysis, it is shown that the maximum sulfur content (16.5 wt%) was obtained with the Sibunit-4® catalyst oxidized at 400 °C. The incorporation of a sulfate group has been proven by the elemental analysis and Fourier-transform infrared spectroscopy. The molecular weight distribution has been examined by gel permeation chromatography. It has been demonstrated that the solid catalysts used in the sulfation process causes hydrolysis reactions and reduces the molecular weight and polydispersity index. It has been established by the thermal analysis that sulfated lignin is thermally stabile at temperatures of up to 200 °C. According to the atomic force microscopy data, the surface of the investigated film consists of particles with an average size of 50 nm. The characteristics of the initial and sulfated β-O-4 lignin model compounds have been calculated and recorded using the density functional theory.

Spruce (Piceaabies) wood hemicelluloses have been obtained by the noncatalytic and catalytic oxidative delignification in the acetic acid-water-hydrogen peroxide medium in a processing time of 3–4 h and temperatures of 90–100 °C. In the catalytic process, the H2SO4, MnSO4, TiO2, and (NH4)6Mo7O24 catalysts have been used. A polysaccharide yield of up to 11.7 wt% has been found. The hemicellulose composition and structure have been studied by a complex of physicochemical methods, including gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, and thermogravimetric analysis. The galactose:mannose:glucose:arabinose:xylose monomeric units in a ratio of 5:3:2:1:1 have been identified in the hemicelluloses by gas chromatography. Using gel permeation chromatography, the weight average molar mass Mw of hemicelluloses has been found to attain 47,654 g/mol in noncatalytic delignification and up to 42,793 g/mol in catalytic delignification. Based on the same technique, a method for determining the α and k parameters of the Mark–Kuhn–Houwink equation for hemicelluloses has been developed; it has been established that these parameters change between 0.33–1.01 and 1.57–472.17, respectively, depending on the catalyst concentration and process temperature and time. Moreover, the FTIR spectra of the hemicellulose samples contain all the bands characteristic of heteropolysaccharides, specifically, 1069 cm−1 (C–O–C and C–O–H), 1738 cm−1 (ester C=O), 1375 cm−1 (–C–CH3), 1243 cm−1 (–C–O–), etc. It has been determined by the thermogravimetric analysis that the hemicelluloses isolated from spruce wood are resistant to heating to temperatures of up to ~100 °C and, upon further heating, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses has been examined using the compounds simulating the 2,2-diphenyl-2-picrylhydrazyl free radicals.

Xanthan is an important polysaccharide with many beneficial properties. Sulfated xanthan derivatives have anticoagulant and antithrombotic activity. This work proposes a new method for the synthesis of xanthan sulfates using sulfamic acid. Various N-substituted ureas have been investigated as process activators. It was found that urea has the greatest activating ability. BBD of xanthan sulfation process with sulfamic acid in 1,4-dioxane has been carried out. It was shown that the optimal conditions for the sulfation of xanthan (13.1 wt% sulfur content) are: the amount of sulfating complex per 1 g of xanthan is 3.5 mmol, temperature 90 °C, duration 2.3 h. Sulfated xanthan with the maximum sulfur content was analyzed by physicochemical methods. Thus, in the FTIR spectrum of xanthan sulfate, in comparison with the initial xanthanum, absorption bands appear at 1247 cm−1, which corresponds to the vibrations of the sulfate group. It was shown by GPC chromatography that the starting xanthan gum has a bimodal molecular weight distribution of particles, including a high molecular weight fraction with Mw > 1000 kDa and an LMW fraction with Mw < 600 kDa. It was found that the Mw of sulfated xanthan gum has a lower value (~612 kDa) in comparison with the original xanthan gum, and a narrower molecular weight distribution and is characterized by lower PD values. It was shown by thermal analysis that the main decomposition of xanthan sulfate, in contrast to the initial xanthan, occurs in two stages. The DTG curve has two pronounced peaks, with maxima at 226 and 286 °C.