Depolymerization of Pine Wood Organosolv Lignin in Ethanol Medium over NiCu/SiO2 and NiCuMo/SiO2 Catalysts: Impact of Temperature and Catalyst Composition.

The process of thermocatalytic conversion of pine ethanol lignin in supercritical ethanol was studied over NiCu/SiO2 and NiCuMo/SiO2 catalysts bearing 8.8 and 11.7 wt.% of Mo. The structure and composition of ethanol lignin and the products of its thermocatalytic conversion were characterized via 2D-HSQC NMR spectroscopy, GC-MC. The main aromatic monomers among the liquid products of ethanol lignin conversion were alkyl derivatives of guaiacol (propyl guaiacol, ethyl guaiacol and methyl guaiacol). The total of the monomers yield in this case was 12.1 wt.%. The temperature elevation up to 350 °C led to a slight decrease in the yield (to 11.8 wt.%) and a change in the composition of monomeric compounds. Alkyl derivatives of pyrocatechol, phenol and benzene were observed to form due to deoxygenation processes. The ratio of the yields of these compounds depended on the catalyst, namely, on the content of Mo in the catalyst composition. Thus, the distribution of monomeric compounds used in various industries can be controlled by varying the catalyst composition and the process conditions.

Preparation and Characterization of di- and Tricarboxylic Acids-Modified Arabinogalactan Plasticized Composite Films.

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.

Sulfation of Birch Wood Microcrystalline Cellulose with Sulfamic Acid Using Ion-Exchange Resins as Catalysts.

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.

New Azo Derivatives of Ethanol Lignin: Synthesis, Structure, and Photosensitive Properties.

Water-soluble azo derivatives of lignin were synthesized by the azo coupling reaction using organosolv ethanol lignin and diazonium salts based on sulfanilic acid and p-nitroaniline. The structure of azo derivatives of lignin were studied by nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and gel permeation chromatography. It was found that the azobenzene bonds formed in the azo coupling reaction of macromolecules impart the photosensitive properties to the synthesized polymers via cis-trans photoisomerization of the diazobenzene group. It was shown experimentally that the synthesized polymers exhibited good solubility both in the aqueous media in a wide (2-12) pH range and in DMSO and THF organic solvents, which opens up new prospects for their application.

Microfibrillated Cellulose with a Lower Degree of Polymerization; Synthesis via Sulfuric Acid Hydrolysis under Ultrasonic Treatment.

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.

Thrombin and Factor Xa Hydrolysis of Chromogenic Substrates in the Presence of Sulfated Derivatives of Galactomannan and Galactoglucomannan Natural Gels.

Polysaccharides are important structural components of all plant species. Gel-like polysaccharides have found wide application in various fields, including medicine, construction, and the food industry. In the present work, galactomannan and galactoglucomannan gel-like polysaccharides were modified with sulfate groups and their anticoagulant activity was studied. Sulfation with chlorosulfonic acid in pyridine and with sulfamic acid in pyridine and a sulfamic acid-urea deep eutectic solvent were used as synthesis routes. The resulting gel-like polysaccharide sulfates were studied by elemental analysis, Fourier-transform infrared spectroscopy, and gel permeation chromatography. It was established that the anticoagulant effect of sulfated galactoglucomannan (SGGM) and galactomannan (SGM-1 and SGM-2) is related to an independent antithrombin-independent decrease in the amidolytic activity of thrombin and factor Xa. It is shown that the inhibitory activity of SGGM and SGM-2 against the collagen-induced platelet aggregation can be an additional factor in selecting compounds that are most promising for modifying polymer surfaces to ensure resistance to blood clotting.

Larix Sibirica Arabinogalactan Hydrolysis over Zr-SBA-15; Depolymerization Insight.

Arabinogalactan depolymerization over solid Zr-containing SBA-15-based catalyst was studied via HPLC, GPC, and theoretical modeling. Arabinogalactans (AG) are hemicelluloses mainly present in larch wood species, which can be extracted on an industrial scale. The application of solid acid catalysts in the processes of hemicellulose conversion can exclude serious drawbacks such as equipment corrosion, etc. Characterization of 5%Zr-SBA-15 confirmed the successful formation of the mesoporous structure inherent to SBA-15 with fine Zr distribution and strong acidic properties (XRD, XPS, FTIR, pHpzc). Carrying out the process at 130 °C allowed us to achieve total products yield of up to 59 wt%, which is represented mainly by galactose (51 wt%) and minor (less than 9 wt%) presence of arabinose, furfural, 5-HMF, and levulinic acid. The temperature increases up to 150 °C resulted in a total product yield drop down to 37 wt%, making temperature elevation above 130 °C obsolete. According to the theoretical investigations, arabinogalactan depolymerization follows the primary cleavage of the ß(1→3) bonds between the D-galactose units of the main chain, which is also confirmed by GPC.

Composition and Structure of Aspen (Pópulus trémula) Hemicelluloses Obtained by Oxidative Delignification.

In this study, hemicelluloses of aspen wood (Pópulus trémula) were obtained by oxidative delignification in an acetic acid-water-hydrogen peroxide medium at temperatures of 70-100 °C and a process time of 1-4 h. The maximum polysaccharide yield of up to 9.68 wt% was reported. The composition and structure of the hemicelluloses were studied using a complex of physicochemical methods: gas and gel permeation chromatography, Fourier-transform infrared spectroscopy, 2D nuclear magnetic resonance spectroscopy, and thermogravimetric analysis. The xylose, mannose, galactose, and glucose monomer units were identified in the hemicelluloses by gas chromatography. The weight average molecular weight Mw of the products determined by gel permeation chromatography was found to range within 8932-33,142 g/mol. The reported Fourier-transform spectra of the hemicelluloses contain all the bands characteristic of heteropolysaccharides; a weak lignin absorption signal in the spectra at 1500-1510 cm-1 is attributed to a minor content of phenolic fragments in the structure of the obtained hemicelluloses. The use of thermogravimetric analysis established that the hemicelluloses isolated from aspen wood are resistant against heating to temperatures of up to 90-100 °C and, upon further heating up to 400 °C, start destructing at an increasing rate. The antioxidant activity of the hemicelluloses was examined using the compounds that mimic free radicals (1,1-diphenyl-2-picrylhydrazyl) and hydroxyl radicals (salicylic acid). It was found that the activity of all polysaccharides in neutralizing DPPH and hydroxyl radicals is lower than the absorption capacity of vitamin C at all the tested concentrations (0.5, 2, and 5 mg/mL) and attains 81.7 and 82.9%, respectively.

An Efficient Method of Birch Ethanol Lignin Sulfation with a Sulfaic Acid-Urea Mixture.

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.

Sulfation of Wheat Straw Soda Lignin with Sulfamic Acid over Solid Catalysts.

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 ß-O-4 lignin model compounds have been calculated and recorded using the density functional theory.

Catalytic Sulfation of Betulin with Sulfamic Acid: Experiment and DFT Calculation.

Betulin is an important triterpenoid substance isolated from birch bark, which, together with its sulfates, exhibits important bioactive properties. We report on a newly developed method of betulin sulfation with sulfamic acid in pyridine in the presence of an Amberlyst®15 solid acid catalyst. It has been shown that this catalyst remains stable when being repeatedly (up to four cycles) used and ensures obtaining of sulfated betulin with a sulfur content of ~10%. The introduction of the sulfate group into the betulin molecule has been proven by Fourier-transform infrared, ultraviolet-visible, and nuclear magnetic resonance spectroscopy. The Fourier-transform infrared (FTIR) spectra contain absorption bands at 1249 and 835-841 cm-1; in the UV spectra, the peak intensity decreases; and, in the nuclear magnetic resonance (NMR) spectra, of betulin disulfate, carbons С3 and С28 are completely shifted to the weak-field region (to 88.21 and 67.32 ppm, respectively) with respect to betulin. Using the potentiometric titration method, the product of acidity constants K1 and K2 of a solution of the betulin disulfate H+ form has been found to be 3.86 × 10-6 ± 0.004. It has been demonstrated by the thermal analysis that betulin and the betulin disulfate sodium salt are stable at temperatures of up to 240 and 220 °C, respectively. The density functional theory method has been used to obtain data on the most stable conformations, molecular electrostatic potential, frontier molecular orbitals, and mulliken atomic charges of betulin and betulin disulfate and to calculate the spectral characteristics of initial and sulfated betulin, which agree well with the experimental data.

Molecular Characteristics and Antioxidant Activity of Spruce (Picea abies) Hemicelluloses Isolated by Catalytic Oxidative Delignification.

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.

Food Xanthan Polysaccharide Sulfation Process with Sulfamic Acid.

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.

Sulfation of Diethylaminoethyl-Cellulose: QTAIM Topological Analysis and Experimental and DFT Studies of the Properties.

Sulfated cellulose derivatives are biologically active substances with anticoagulant properties. In this study, a new sulfated diethylaminoethyl (DEAE)-cellulose derivative has been obtained. The effect of a solvent on the sulfation process has been investigated. It is shown that 1,4-dioxane is the most effective solvent, which ensures the highest sulfur content in DEAE-cellulose sulfate under sulfamic acid sulfation. The processes of sulfamic acid sulfation in the presence of urea in 1,4-dioxane and in a deep eutectic solvent representing a mixture of sulfamic acid and urea have been compared. It is demonstrated that the use of 1,4-dioxane yields the sulfated product with a higher sulfur content. The obtained sulfated DEAE-cellulose derivatives have been analyzed by Fourier transform infrared spectroscopy, X-ray diffractometry, and scanning electron and atomic force microscopy, and the degree of their polymerization has been determined. The introduction of a sulfate group has been confirmed by the Fourier transform infrared spectroscopy data; the absorption bands corresponding to sulfate groups have been observed in the ranges of 1247-1256 and 809-816 cm-1. It is shown that the use of a deep eutectic solvent leads to the side carbamation reactions. Amorphization of DEAE-cellulose during sulfation has been demonstrated using X-ray diffractometry. The geometric structure of a molecule in the ground state has been calculated using the density functional theory with the B3LYP/6-31G(d, p) basis set. The reactive areas of DEAE-cellulose and its sulfated derivatives have been analyzed using molecular electrostatic potential maps. The thermodynamic parameters (heat capacity, entropy, and enthalpy) of the target sulfation products have been determined. The HOMO-LUMO energy gap, Mulliken atomic charges, and electron density topology of the title compound have been calculated within the atoms in molecule theory.

Modification of Arabinogalactan Isolated from Larix sibirica Ledeb. into Sulfated Derivatives with the Controlled Molecular Weights.

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.

Interaction of Rare-Earth Metals and Some Perfluorinated ß-Diketones.

In this work, we demonstrate the fundamental relationships between stability constants and periodic, acid-base, and structural parameters for complexes of some 1,3-diketones. The four analogues of hexafluoroacetylacetone-2-thenoyltrifluoroacetone, 2-furoyltrifluoroacetone, benzoyltrifluoroacetone, and 2-naphthyltrifluoroacetone-have been studied as chelating ligands for 16 rare-earth metals (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) in aqueous solutions. Systems have been investigated spectrophotometrically using a multiwave nonlinear least-squares regression algorithm for data processing. Conditional stability constants were obtained for a wide pH region (2.0-5.4) at constant ionic strength (I = 0.5 M, NaCl). To receive the apparent ("true") equilibrium parameters, acid-base and keto-enol characteristics of the studied ligands have been described and revised for specific conditions. Dissociation constants were obtained in citrate-phosphate buffer media and protonation parameters were received in concentrated hydrochloric acid by the Cox-Yates method. The apparent formation constants for monocomplex species were obtained as thermodynamic invariants (depend only on the temperature) for each ligand and lie from 4.2 to 12.7 logarithmic units. Although the studied ligands have similar values of pKa, the stabilities of their complexes vary considerably. Systematic analysis of 64 apparent stability constants demonstrates that the force of interaction between the metals and nonsymmetric ß-diketones increases as 2-furoyltrifluoroacetone < 2-thenoyltrifluoroacetone < benzoyltrifluoroacetone < 2-naphthyltrifluoroacetone. The studied ligands display varying degrees of the correlation between the periodic parameters and formation constants. Naphthyltrifluoroacetone and its complexes with heavy lanthanides exhibit a clear trend in properties with increasing ionic potential. In general, the received set of data can be described from purely electrostatic grounds within the framework of the periodic law. Spectral, keto-enol, acid-base, and complexing properties were reproduced using density functional theory modeling and explain some of the regularities discovered.

Theoretical and experimental study of guar gum sulfation.

The synthesis of guar gum sulfates by a complex of sulfur trioxide with 1,4-dioxane was studied. The influence of temperature, process duration, and the volume of chlorosulfonic acid on the degree of substitution of guar gum sulfates was studied. The sulfation process has been optimized using the Box-Behnken design. It was shown that the optimal conditions for sulfation of guar gum with a complex of sulfur trioxide-1.4-dioxane: temperature 60 °C, duration 2.9 h, and a volume of chlorosulfonic acid of 3.1 ml. Sulfate groups embedding into the structure of guar gum was confirmed by elemental analysis and FTIR. The initial and sulfated guar gum were also characterized by methods: X-ray diffraction, scanning electron microscopy, and gel permeation chromatography. Using X-ray diffraction, it was shown that amorphization of guar gum occurs during sulfation. Using scanning electron microscopy, it was shown that the morphology of guar gum changes in the process of sulfation. Using gel permeation chromatography, it was shown in the process of guar gum sulfation by a complex of sulfur trioxide with 1,4-dioxane, the molecular weight decreases from 600 to 176 kDa. The geometric parameters of all complexes were carried out by using the DFT/B3PW91 method with a 6-31 + G (d,p) basis set. These structures are optimized to predict the important properties of a theme. MEP with contour map has been performed to obtain the electronic properties. Frontier molecular orbital HOMO-LUMO orbital diagram has been obtained for different energy levels and their band gap energies have been computed.