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 M_w > 1000 kDa and an LMW fraction with M_w < 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.

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 M_w 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.

Imidazole derivatives have found wide application in organic and medicinal chemistry. In particular, benzimidazoles have proven biological activity as antiviral, antimicrobial, and antitumor agents. In this work, we experimentally and theoretically investigated N-Butyl-1H-benzimidazole. It has been shown that the presence of a butyl substituent in the N position does not significantly affect the conjugation and structural organization of benzimidazole. The optimized molecular parameters were performed by the DFT/B3LYP method with 6-311++G(d,p) basis set. This level of theory shows excellent concurrence with the experimental data. The non-covalent interactions that existed within our compound N-Butyl-1H-benzimidazole were also analyzed by the AIM, RDG, ELF, and LOL topological methods. The color shades of the ELF and LOL maps confirm the presence of bonding and non-bonding electrons in N-Butyl-1H-benzimidazole. From DFT calculations, various methods such as molecular electrostatic potential (MEP), Fukui functions, Mulliken atomic charges, and frontier molecular orbital (HOMO-LUMO) were characterized. Furthermore, UV-Vis absorption and natural bond orbital (NBO) analysis were calculated. It is shown that the experimental and theoretical spectra of N-Butyl-1H-benzimidazole have a peak at 248 nm; in addition, the experimental spectrum has a peak near 295 nm. The NBO method shows that the delocalization of the aσ-electron from σ (C1–C2) is distributed into antibonding σ* (C1–C6), σ* (C1–N26), and σ* (C6–H11), which leads to stabilization energies of 4.63, 0.86, and 2.42 KJ/mol, respectively. Spectroscopic investigations of N-Butyl-1H-benzimidazole were carried out experimentally and theoretically to find FTIR vibrational spectra.

The process of sulfation of arabinogalactan—a natural polysaccharide from Larix sibirica Ledeb.—with sulfamic acid in 1,4-dioxane using different activators has been studied for the first time. The dynamics of the molecular weight of sulfated arabinogalactan upon variation in the temperature and time of sulfation of arabinogalactan with sulfamic acid in 1,4-dioxane has been investigated. It has been found that, as the sulfation time increases from 10 to 90 min, the molecular weights of the reaction products grow due to the introduction of sulfate groups without significant destruction of the initial polymer and sulfation products. Sulfation at 95 °C for 20 min yields the products with a higher molecular weight than in the case of sulfation at 85 °C, which is related to an increase in the sulfation rate; however, during the further process occurring under these conditions, sulfation is accompanied by the destruction and the molecular weight of the sulfated polymer decreases. The numerical optimization of arabinogalactan sulfation process has been performed. It has been shown that the optimal parameters for obtaining a product with a high sulfur content are a sulfamic acid amount of 20 mmol per 1 g of arabinogalactan, a process temperature of 85 °C, and a process time of 2.5 h.

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.

This study examines galactoglucomannan, a well-studied biopolymer isolated from Siberian spruce (Picea obovata Ledeb). Due to its structure, abundant with hydroxyl groups, galactoglucomannan’s properties, such as heavy-metal ion affinity, are considered to be mediocre. Nevertheless, there are various ways to enhance its functionality via oxidative TEMPO/NaBr/NaOCl processing. This work is concerned with the determination of the oxidation effect on the structure and performance properties, such as thermal decomposition behavior, antioxidant activity, and selective heavy-metal sorption. In the results, TEMPO-oxidized galactoglucomannan yields vary in the range of 78.3 ± 6.4 wt.%. The carboxylate group in the oxidized derivative represents up to 0.084 g/1 g of the sample. According to antioxidant activity tests, the oxidized galactoglucomannan exceeds the initial sample in terms of hydroxyl radical scavenging ability. The spectral characteristics of the initial and oxidized galactoglucomannan samples reveal the differences in absorption units (1725, 1610, and 1371 cm⁻¹). The preservation of the polymeric structure was confirmed by the gel permeation chromatography analysis results. The heavy-metal ion capacity of galactoglucomannan is higher for the oxidized derivative, which demonstrated Cd²⁺, Fe²⁺, Cu²⁺, and Pb²⁺ adsorption values of 166.8 mg/g, 142.8 mg/g, 150.0 mg/g, and 199.2 mg/g, accordingly. The obtained result of the competitive heavy-metal ion adsorption of oxidized galactoglucomannan also exceeds its initial form, as characterized by its summary 143.1 mg/g capacity.