Inhibiting properties of lignin

Inhibitory efficacy has been determined by the method of the weight losses of steel in acid with native lignin, hydrolysis lignin, ammoniated native lignin, chlorinated hydrolysis lignin, and ammoniated hydrolysis lignin, and without these additives. It has been established that the efficacy of lignin and its modifications as inhibitors of acid corrosion increases with a rise in the number of carboxy groups in the macromolecule, and therefore the ammoniated hydrolysis lignin is the most effective.Central Scientific-Research and Planning Technological Institute for the Mechanization and Electrification of Animal Husbandry of the Southern Zone of the USSR. Zaporozh'e Astrakhan Technical Institute of the Fisheries Industry and Economy, Astrakhan'. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 378–380, May–June, 1983.     

Phosphorylation of hydrolysis lignin by dialkyl phosphorochloridates

It has been established that the phosphorylation of lignin by dialkyl phosphorochloridates takes place through the hydroxy groups of the lignin macromolecule.Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 750–752, September–October, 1997.     

The reaction of nitrolignin with ammonia

The reaction of nitrolignin with ammonia has been studied. It has been established that it takes place mainly through the carbonyl and carboxy groups of the lignin. A dark brown product with a high nitrogen content readily soluble in water and exhibiting biological activity was obtained. On the basis of the results of elementary and functional analyses, a semiempirical formula has been calculated for the substance obtained, and its viscosity and electrical conductivity have been determined. The molecular weight, determined by the sedimentation method in an ultracentrifuge, was more than 60,000. It was established by gel chromatography that the product of the interaction of nitrolignin with ammonia was polydisperse.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, Vol. 5, pp. 827–829, November–December, 1985.     

A study of the process of lignification of one-year willow wood

Conclusions 1. The content of lignin in the wood ofSalix viminalis andSalix acutifolia increases with the growth of the shoots during shortened days and also in drier climatic periods.2. The monosaccharides, glucose, fructose, and arabinose take part in the synthesis of the lignin of young wood ofSalix viminalis andSalix acutifolia. The formation of lignin of one-year willow wood takes place from May to January (with a maximum in June–July). The content of methoxyl groups in it gradually rises.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 6, pp. 546–550, 1969     

Study of the fractional composition of the dioxane lignin from the cotton plant

Summary 1. The dioxane lignin of ripe cotton-plant stems has been separated into six fractions of different molecular weights which were fairly homogeneous and differed considerably in their molecular weights.2. It follows from the semiempirical formulas that in all the fractions guaiacyl structural units predominated. The chemical nonidentity of the fractions is shown by the different amounts of functional groups in the phenylpropane structural units and by the relative optical densities of the main bands in the IR spectra of the fractions.3. The low-molecular-weight fraction differed markedly from the others by a higher content of carbohydrates bound to the lignin and by a greater degree of oxidation.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 69–74, January–February, 1979.     

Enzymatic oxidation of lignin and compounds modeling it. III. Formation of singlet oxygen in the peroxidase oxidation of lignin

The main emitters of radiation in the aerobic oxidation of lignin are the carbonyl groups in an excited state and singlet oxygen. It has been shown that the main source of O₂(¹) may be the radical anion O^–·₂. Singlet oxygen and the radical anion are by-products of the radical oxidation of lignin.Siberian Scientific-Research Institute of Cellulose and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 510–514, July–August, 1984.     

An IR study of organosolvent lignin

The functional composition of lignin recovered from spruce wood and treated with alkali in aqueous and aqueous-ethanol medium and that of lignins recovered from alkaline cooking solutions in the presence of ethanol were studied by IR spectroscopy. The influence of ethanol on the content of the main functional groups in lignin was examinated.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 9, 2004, pp. 1547–1550.Original Russian Text Copyright © 2004 by Skrebets, Bogolitsyn, Kosyakov, Verbitskaya.     

Valorization of Rice Straw via Hydrotropic Lignin Extraction and Its Characterization

Rice straw hydrotropic lignin was extracted from p-Toluene sulfonic acid (p-TsOH) fractionation with a different combined delignification factor (CDF). Hydrotropic lignin characterization was systematically investigated, and alkaline lignin was also studied for the contrast. Results showed that the hydrotropic rice straw lignin particle was in nanometer scopes. Compared with alkaline lignin, the hydrotropic lignin had greater molecular weight. NMR analysis showed that β-aryl ether linkage was well preserved at low severities, and the unsaturation in the side chain of hydrotropic lignin was high. H units and G units were preferentially degraded and subsequently condensed at high severity. High severity also resulted in the cleavage of part β-aryl ether linkage. ³¹P-NMR showed the decrease in aliphatic hydroxyl groups and the increasing carboxyl group content at high severity. The maximum weight loss temperature of the hydrotropic lignin was in the range of 330–350 °C, higher than the alkaline lignin, and the glass conversion temperature (T_g) of the hydrotropic lignin was in the range of 107–125 °C, lower than that of the alkaline lignin. The hydrotropic lignin has high β-aryl ether linkage content, high activity, nanoscale particle size, and low T_g, which is beneficial for its further valorization.     

Study of the IR spectra of the products of the ethanolysis of oak and pine lignins

Summary The IR spectra of a number of compounds formed in the ethanolysis of the lignin of foliate and coniferous species have been studied using samples of ethanol lignin, vanillin, syringic aldehyde, p-hydroxybenzaldehyde, guaiacylacetone, coniferyl and sinapic aldehydes, vanilloyl methyl ketone, -hydroxypropiovanillone, -ethoxypropiosyringone, and vanillic and gallic acids. Differences in the absorption at 1330–1340 cm^–1 have been found in the spectra of samples of ethanol lignin from oak and pine. Oak lignin has a strong maximum which is absent in pine lignin. Thus, the lignins of foliate and confierous species can be distinguished by the absorption in the spectral region from 1330 to 1340 cm^–1.Khimiya Prirodnykh Soedinenii, Vol. 3, No. 2, pp. 208–213, 1967     

Highly hydrophobic sisal chemithermomechanical pulp (CTMP) paper by fluorotrimethylsilane plasma treatment

Fluorinated thin layers were created on chemithermomechanical pulp (CTMP) sisal paper surfaces with fluorotrimethylsilane (FTMS) radio frequency-plasma conditions. It was found that the FTMS-discharge environments caused implantation of fluorine and –Si(CH₃) _x groups into the surface layers of the paper substrates. Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy and Electron Spectroscopy for Chemical Analysis, as well as Atomic Force Microscopy and Scanning Electron Microscopy analyses revealed a smooth surface for the FTMS plasma-treated paper, apparently covered completely with a cross-linked polymerized network. Although the plasma reaction takes place with the cellulose, hemicelluloses and lignin, it appears that the chemical linkage is mainly to the lignin component on the CTMP paper surface by means of mainly C–O–Si–F, with some C–Si–F structures. The CTMP fibers apparently have a high lignin surface concentration. The water absorption for the plasma-treated CTMP paper was reduced from greater than 300 to 17 g of water/m² and the contact angle increased from less than 15° to greater than 120° the strength properties were only slightly reduced and the brightness was essentially unaffected with the FTMS plasma treatment.     

Quantitative1H and13C NMR spectroscopies of cottonplant dioxane lignin

A comparative analysis has been made of the dioxane lignins of the stems, seedling shoots, and seed coats of the cotton plant. The ratio of p-hydroxyaromatic, guaiacyl, and syringyl units in the macromolecules of the lignins has been determined, and so have the amounts of functional groups and bonds. It has been established that the main difference between the dioxane lignins from seedling shoots and seed coats of the cotton plant, on the one hand, and the lignin from the woody stems, on the other hand is a lower content of syringyl and guaiacyl units in the former.Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 798–808, November–December, 1994.     

Destruction of aspen wood by the fungusPhanerochaete sanguinea quantitative1H and13C NMR spectroscopies of biologically degraded lignin

The lignin of mechanically ground aspen wood and lignins isolated from aspen wood attacked by the fungusPhanerochaete sanguinea have been investigated by quantitative¹H and¹³C NMR spectroscopies. It has been shown that the biodestruction of the lignin takes place through the cleavage of alkyl-aryl and aryl-aryl bonds and is accompanied by demethylation (demethoxylation) reactions, and the oxidation of C and C atoms. In addition to reactions in which the C—C bonds are cleaved, the formation of ether bonds has been observed. An interconnection has been shown between the variations in the amount of functional groups, fragments, and the bonds in biolignins and the loss in mass of the wood. A method is proposed for evaluating the carbohydrate content in lignin preparations using the NMR method.Wood Chemistry Branch of the Institute of Organic Chemistry, Siberian Division of the Russian Academy of Sciences, Irkutsk. Irkutsk State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 547–557, July–August, 1994.     

Mild Organosolv Delignification of Residual Aspen Bark after Extractives Isolation as a Step in Biorefinery Processing Schemes

European aspen (Populus tremula (L.) (Salicaceae)) bark is a promising raw material in multi-step biorefinery schemes due to its wide availability and higher content of secondary metabolites in comparison to stem wood biomass. The main objective of this study was to investigate the major cell wall component-enriched fractions that were obtained from aspen bark residue after extractives isolation, primarily focusing on integration of separated lignin fractions and cellulose-enriched bark residue into complex valorization pathways. The “lignin first” biorefinery approach was applied using mild organosolv delignification. The varying solvent systems and process conditions for optimal delignification of residual aspen bark biomass were studied using a response surface methodology approach. The conditions for maximum process desirability at which the highest amount of lignin-enriched fraction was separated were as follows: 20-h treatment time at 117 °C, butanol/water 4:1 (v/v) solvent system with solid to liquid ratio of 1 to 10. At optimal separation conditions, lignin-enriched fraction exhibited a higher content of β–O–4 linkages vs. C–C linkages content in its structure as well as a high amount of hydroxyl groups, being attractive for its further valorization. At the same time, the content of glucose in products of cellulose-enriched residue hydrolysis was 52.1%, increased from 10.3% in untreated aspen bark. This indicates that this fraction is a promising raw material for obtaining cellulose and fermentable glucose. These results show that mild organosolv delignification of extracted tree bark can be proposed as a novel biorefinery approach for isolation of renewable value-added products with various application potentials.     

On the character of the ethoxyl groups introduced into lignin when it is niteated in alcohol

Conclusions The ethoxyl groups which enter into the lignin during alcoholic nitration are formed by the etherification of its arylcarbinol groups.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1366–1368, June, 1969.     

An investigation of the fractional composition of dioxane lignin of the cotton plant by the PMR method

Analysis of the PMR spectra of six fractions of the dioxane lignins of the cotton plant differing considerably in molecular weight has confirmed their chemical nonidentity. It has been established that the low-molecular-weight fractions are less condensed than the high-molecular-weight fractions. It has been found that aliphatic OH groups are approximately evenly distributed between the - and -C atoms of the lignin side chain.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 116–120, January–February, 1980.     

Metabolism of acetophenone compounds of the fungus Sportorichum pulverulentum

With the aim of revealing the specific reactions of biotransformation under lignolytic conditions, the metabolic transformation bySporotrichum pulverulentum of a number of acetophenone compounds not previously investigated that model fragments of the lignin molecule has been studied. It has been established that the metabolism of 4-hydroxyacetophenone 3-O--D-glucopyranoside takes place as a sequence of processes involving deglucosylation, the methylation of free phenolic hydroxy groups with the formation of methylated intermediates, and the further hydroxylation of the m-methylated metabolite.Irkutsk Institute of Organic Chemistry, Siberian Branch, USSR Academy of Sciences. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 987–902, November–December, 1987.     

THM PyGC–MS of wood fragment and vegetable fibre forensic samples

Wood fragments and vegetable fibres were investigated using thermally assisted hydrolysis and methylation with pyrolysis gas chromatography–mass spectrometry (THM PyGC–MS). Multiple ion chromatography was used to decrease the interference from cellulosic peaks, and to obtain greater resolution between the lignin peaks. Forty-four wood samples were analysed using THM PyGC–MS. The wood fragments were able to be differentiated into angiosperms (hardwoods) and gymnosperms (softwoods) using principle component analysis (PCA), hierarchical cluster analysis (HCA), and the ratio of syringyl to guaiacyl lignin fragments (S/G ratio). PCA and HCA also differentiated several Monterey pine samples from the rest of the gymnosperms, primarily by the presence of β-pinene, an extractive compound. Other gymnosperm species and the individual angiosperm species were unable to be differentiated. A pilot study investigating the use of THM PyGC–MS for the analysis of vegetable fibres in forensic science found that the fibre types tended to group into two clusters, with one containing cotton, hemp and linen; and the other consisting of hessian, sisal, jute and coir. The seagrass sample was able to be differentiated from both groups. These groups were well separated using PCA, HCA and by the ratio of cinnamyl phenolic derivatives to guaiacyl lignin derivatives (C/G ratio). Some grouping of each fibre type was evident within each cluster, however the separation between the clusters was insufficient to differentiate them using these statistical techniques. THM PyGC–MS of vegetable fibres showed some potential for future use in forensic science.     

Formation of peroxide compounds on the oxidation of lignin by oxygen in an organic solvent

The results are given of a determination of the steady-state concentrations of peroxide compounds on the oxidation of lignin by oxygen in dioxane. An iodometric method of determining peroxides was used, with spectrophotometric control of the amount of iodine formed. It was established that the achievable steady-state concentration of peroxide compounds on the oxidation of lignin is 0.28–0.44 wt. % of O_act (oxygen pressure 1 atm, temperature 50–80°C). With a rise in the temperature, the steady-state concentration of peroxide compounds decreased. The addition of water (30 vol. %) to the organic solvent led to an increase in the rate of accumulation of peroxide compounds. It has been shown that the presence of alkaline and acidic catalysts exerts no appreciable influence on the achievable steady-state concentration and the rate of accumulation of peroxide compounds during the oxidation of lignin.Bratsk Industrial Institute. All-Union Scientific Production Combine of the Pulp and Paper Industry, Leningrad. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 413–417, May–August, 1992.     

Dioxane lignin from shoots of the cotton plant of variety 108-F. I

The dioxane lignin has been isolated by Pepper's method from two-week shoots of the cotton plant of variety 108-F and has been separated into two fractions — insoluble and soluble in ether — DLA-A and DLA-B, respectively. It has been shown that in the early stage of development of the cotton plant a low-molecular-weight lignin with a low degree of methoxylation and distinctly different from the lignin from ripe stems of the same cotton plant is synthesized.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 96–98, January–February, 1984.     

Nitration of lignin isolated from spruce wood by mechanical grinding

Summary 1. The nitration of spruce lignin obtained by mechanical grinding has been carried out with nitric acid in an anhydrous medium under heterogeneous and homogeneous conditions. Fractionation of the nitrolignin has been carried out and the elementary and functional composition of the fractions has been determined; the mean semi-empirical formulas of the C₉ structures have been calculated for both fractions. It has been shown that, depending on the nitration conditions, from one to two nitro groups enter the C₆-C₃ structural element of nitrolignin and, with an excess of HNO₃, nitrate groups as well.The fall in the content of OCH₃ groups corresponds to the content of phenolic hydroxyl groups in the initial MGL and can be explained by the demethylation of the guaiacyl structures of the lignin on nitration.Khimiya Prirodnykh Soedinenii, Vol. 2, No. 1, pp. 58–65, 1966