Oxidation of lignin in aqueous alkaline solution

Chemistry of Natural Compounds - The hydrogenolysis and hydrolysis of lignin in an aqueous alkaline medium must be considered as an oxidative degradation of the lignin macromolecule by hydroxyl...     

Hydrogenolysis of rice husk protolignin. II

It has been established that the partial hydrogenolysis of rice husk protolignin (RHP) takes place at a temperature of 180°C and an initial hydrogen pressure of 10 atm in an alkaline medium. Conditions have been selected under which the greatest yield of low-molecular-weight products (91% on the Komarov lignin) is obtained: hydrogenolysis in an alkaline medium in the presence of an anthraquinone (AQ) catalyst. The addition of AQ increases the yield of low-molecular-weight products by a factor of 1.8. Semiempirical formulas have been derived for incompletely hydrolyzed lignin residues. A study of the molecular-weight distribution of these lignins has shown that they are polydisperse. It has been established that in the process of hydrogenolysis AQ promotes the demethoxylation of structural units with syringyl nuclei.Institute of the Chemistry of Plant Substances of the Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 734–738, September–October, 1987.     

Hydrogenolysis of Willst?tter lignin

Summary 1. The hydrogenolysis of Willstätter spruce lignin has been performed under the optimum conditions. It has been shown that on hydrogenolysis in an aqueous alkaline medium in the presence of an inhibitor (phenol) the lignin macromolecules can be converted into low-molecular-weight ether-soluble products with a yield of about 80%.2. A comparative study of the ether-soluble fractions of Willstätter spruce lignin and hydrolysis spruce lignin has shown that hydrogenolysis takes place similarly in the two cases: the yields of phenols and the proportion of cresols in them are similar. In the Willstätter spruce lignin, the yield of acids is higher and that of neutral products lower than in the hydrolysis spruce lignin.3. Investigations of the group compositions of the hydrogenolysis products and of model substances have permitted the hypothesis that the Willstätter lignin contains a considerable amount of biphenyl structures.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 106–112, January–February, 1972.     

The Role of Sulphate and Phosphate Ions in the Recovery of Benzoic Acid Self-Enhanced Ozonation in Water Containing Bromides

The ozonation of aromatic compounds in low-pH water is ineffective. In an acidic environment, the decomposition of ozone into hydroxyl radicals is limited and insufficient for the degradation of organic pollutants. Radical processes are also strongly inhibited by halogen ions present in the reaction medium, especially at low pH. It was shown that even under such unfavorable conditions, some compounds can initiate radical chain reactions leading to the formation of hydroxyl radicals, thus accelerating the ozonation process, which is referred to as so-called “self-enhanced ozonation”. This paper presents the effect of bromides on “self-enhanced ozonation” of benzoic acid (BA) at pH 2.5. It is the first report to fully and quantitatively describe this process. The presence of only 15 µM bromides in water inhibits ozone decomposition and completely blocks BA degradation. However, the effectiveness of this process can be regained by ozonation in the presence of phosphates or sulphate. The addition of these inorganic salts to the bromide-containing solution helps to recover ozone decomposition and BA degradation efficiency. As part of this research, the fractions of hydroxyl, sulphate and phosphate radicals reacting with benzoic acid and bromides were calculated.     

Hydrogenolysis of rice husk lignins

The hydrogenolysis of the protolignin, the hydrolysis lignin, and the dioxane lignin of rice husks in the presence of demethylated lignin as catalyst has been studied. The breakdown of the lignins into low-molecular-mass compounds took place with yields comparable with those obtained by hydrogenolysis using other catalysts.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 611–613, July–August, 1995. Original article submitted November 21, 1994.     

Hydrogenolysis of rice husk protolignin. II

It has been established that the partial hydrogenolysis of rice husk protolignin (RHP) takes place at a temperature of 180°C and an initial hydrogen pressure of 10 atm in an alkaline medium. Conditions have been selected under which the greatest yield of low-molecular-weight products (91% on the Komarov lignin) is obtained: hydrogenolysis in an alkaline medium in the presence of an anthraquinone (AQ) catalyst. The addition of AQ increases the yield of low-molecular-weight products by a factor of 1.8. Semiempirical formulas have been derived for incompletely hydrolyzed lignin residues. A study of the molecular-weight distribution of these lignins has shown that they are polydisperse. It has been established that in the process of hydrogenolysis AQ promotes the demethoxylation of structural units with syringyl nuclei.     

Hydrogenolysis of rice husk lignin. IV

The hydrogenolysis of rice husk protolignin and of rice husk hydrolysis lignin in the presence of catalyst D-101, which is used in the hydrocracking of petroleum, has been studied. A substantial amount of products with syringyl structures has been found in the lignin cleavage products. The hydrogen content of the hydrol lignins isolated was considerably higher than that of the analogous lignins obtained on hydrogenolysis with the use of other catalysts.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan. Scientific-Research Chemical and Technical Institute of the Medical and Microbiological Industry, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 602–605, July–August, 1993.     

Radiolysis of Aqueous Solutions of Poly(ethylene oxide) at 77 K

Low-temperature (77 K) γ-radiolysis of aqueous solutions of poly(ethylene oxide) was studied by ESR spectroscopy. Trapped electrons, hydroxyl radicals, and -CH₂-ĊH-O- radicals were identified as principal paramagnetic products of radiolysis. It was shown that an increase in the polymer concentration in solution led to a growth in number of trapped electrons and -CH₂-ĊH-O- macroradicals. The decay of hydroxyl radicals occurring at 110–115 K was accompanied by the formation of -CH₂-ĊH-O- macroradicals and partial recombination of hydroxyl radicals. Action of visible light resulted in virtually quantitative transformation of trapped electrons into -CH₂-ĊH-O- macroradicals. The radiation-chemical yields of the species trapped at 77 K were estimated and the scheme of radiation-induced chemical processes was suggested.__________Translated from Khimiya Vysokikh Energii, Vol. 39, No. 4, 2005, pp. 243–249.Original Russian Text Copyright © 2005 by Zakurdaeva, Nesterov, Feldman.     

Efficient Degradation of Iopromide by Using Sulfite Activated with Mackinawite

Iopromide (IOP), an iodinated X-ray contrast medium (ICM), is identified as a precursor to iodide disinfection byproducts that have high genotoxicity and cytotoxicity to mammals. ICM remains persistent through typical wastewater treatment processes and even through some hydroxyl radical-based advanced oxidation processes. The development of new technologies to remove ICMs is needed. In this work, mackinawite (FeS)-activated sulfite autoxidation was employed for the degradation of IOP-containing water. The experiment was performed in a 500 mL self-made temperature-controlled reactor with online monitoring pH and dissolved oxygen in the laboratory. The effects of various parameters, such as initial pH values, sulfite dosages, FeS dosages, dissolved oxygen, and inorganic anions on the performance of the treatment process have been investigated. Eighty percent of IOP could be degraded in 15 min with 1 g L⁻¹ FeS, 400 μmol L⁻¹ sulfite at pH 8, and high efficiency on the removal of total organic carbon (TOC) was achieved, which is 71.8% via a reaction for 1 h. The generated hydroxyl and oxysulfur radicals, which contributed to the oxidation process, were identified through radical quenching experiments. The dissolved oxygen was essential for the degradation of IOP. The presence of Cl⁻ could facilitate IOP degradation, while NO₃⁻ and CO₃²⁻ could inhibit the degradation process. The reaction pathway involving H-abstraction and oxidative decarboxylation was proposed, based on product identification. The current system shows good applicability for the degradation of IOP and may help in developing a new approach for the treatment of ICM-containing water.     

Features of the initial stages of the oxidation of lignin by hydrogen peroxide

The kinetics of the initial stages of the oxidation of lignin and of several model compounds have been studied by the stopped-jet method. It has been shown that in the initial stage an intermediate compound is formed with an absorption spectrum close to that of phenoxyl radicals and with a lifetime of 0.013 sec. The high reactivity of the intermediate products leads to a branching of the oxidation process.Siberian Scientific-Research Institute of Pulp and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 516–518, July–August, 1983.     

Features of stable radical generation in lignin on exposure to nitrogen dioxide

The mechanism of stable radical generation in lignin under the action of nitrogen dioxide and NO₂ - air mixture is considered. The formation of phenoxyl, iminoxyl and acylaminoxyl radicals has been detected by EPR. The proposed mechanism involves a primary oxidative reaction of phenol groups with dimers of NO₂ (nitrosyl nitrate) resulting in the formation of phenoxyl radicals and nitric oxide. In the subsequent recombination of phenoxyl radicals and nitric oxide, nitroso compounds and oximes are formed. By reaction of oximes with radicals NO₂, stable iminoxyl radicals are formed. This mechanism is confirmed by kinetic dependencies obtained over a wide range of NO₂ concentrations. From IR spectroscopy measurements it follows that hydroxyl groups of non-phenolic structures of lignin are oxidised to aldehydes producing acylaminoxyl radicals by reaction with NO₂. The kinetic data show that the adsorption of NO₂ on the lignin surface is the rate-determining factor in stable radical formation.     

Pulsed Corona Discharge-Induced Reactions of Acetophenone in Water

The reactions of acetophenone in water by pulsed corona discharges have been investigated to provide fundamental information concerning the reactions of acetophenone in water. Experimental results indicated that photolysis of acetophenone did not involve a hydroxyl radical mechanism and the majority flux of hydroxyl radicals originated from the dissociation of gas-phase oxygen in the plasma channels. The rate constants for photolysis and pyrolysis were determined to be 1.5×10^–7 M-s^–1, 2.2×10^–4 s^–1, respectively. The rate constant for the oxidative reactions was measured as 1.2×10^–7 M-s^–1. Results from this study support the proposal that acetophenone degradation reaction proceed through the oxidative reaction pathway, where molecular oxygen accelerates acetophenone degradation, photolysis, and pyrolysis pathways.     

Applications of ESR and CIDEP to mechanistic studies of lignin chemistry

Using time-resolved CIDEP and conventional ESR as well as optical studies much can be elucidated concerning the initial photochemical reactions of lignin model compounds such as α-guaiacoxyacetoveratrone and α-guaiacoxy-β-propioveratrone. The resulting transient radicals are models for intermediates in the processes of photoyellowing of lignin containing mechanical pulps and papers. Model solution experiments which produce evidence for the roles of free radicals in reductive bleaching of mechanical pulps and in the oxidative aging of papers are also described. The more thorough understanding of these complex processes allows the development of strategies to try to “protect” mechanical pulps and papers from light and thermally induced damage and to “repair” any damage which invevitably occurs.     

The mechanism of the formation of quinonic acids in the oxidation of the bark of the Siberian larch. II

Summary 1. It has been shown by chemical and physicochemical methods of analysis that the oxidation of bark lignin by atmospheric oxygen in nitric acid is accompanied by oxidative-condensation and oxidative-hydrolytic processes.2. Oxidative condensation leads to the formation of a stable intermediate product with a quinoid system of bonds. This complex fragments under the oxidative-hydrolytic action of the medium. The oligomers obtained undergo oxidative-condensation transformations more readily. Such reactions probably take place successively as far as the formation of relatively simple compounds.Siberian Technological Institute, Kransoyarsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 409–412, May–June, 1977.     

Enzymatic oxidation of lignin and compounds modeling it. VI. Analysis of the products of laccase oxidation of lignins

It has been shown that the processes involved in the formation of quinones and the recombination of peroxide radicals take place with the same rate constants. The results obtained give grounds for assuming that the formation of quinones is the result of the recombination and disproportionation of peroxide radicals. A sequence of the reactions taking place in the enzymatic oxidation of lignin is suggested.Siberian Scientific-Research Institute of Cellulose and Cardboard, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 115–118, January–February, 1988.     

Pulse radiolysis studies on [Fe(CN)6]4−−BrO 3 − −CN− system in ethylene glycol — Water solutions

Formation of oxidizing and reducing radicals has been studied by pulse radiolysis of [Fe(CN)₆]^4––BrO ₃ ^– –CN^– system in ethylene glycol — water solvent mixture. Oxidizing ·BrO₂ and BrO radicals formed by electron scavenging with ·BrO ₃ ^– were identified and their reactions were investigated. The reaction of hydroxyl radicals with ethylene glycol leads to formation of reactive radicals with reducing properties and of compounds which reduce slowly in dark the ferricyanide formed in the reaction of ·BrO₂ radical with ferrocyanide.     

Effect of the chemical structure of nitroxyl radicals on their reactivity in the reaction with hydrazobenzene and tetranitromethane

The reaction rate constants of reduction of stable radicals of different classes by hydrazobenzene in hexane at 20C, in the range of 0.4–5·10³ M^–1sec^–1, were determined; a single scale of the oxidative properties of stable nitroxyl radicals was constructed. The rate constants of oxidation of a series of nitroxyl radicals by tetranitromethane in aqueous medium at 20C, in the range of 0.06–10 M^–1·sec^–1, were determined. It was shown that the oxidative properties of the nitroxyl group decrease slightly with an increase in its reducing properties for nitroxyl radicals of the piperidine and imidazoline series in reactions with ascorbic acid and tetra-nitromethane in aqueous medium, respectively.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2575–2582, November, 1990.     

Autocatalytic processes during oxidation of lignin in alkaline media

Results are presented that characterize features of the oxidation of lignin in alkaline media. The prerequisites are considered and proofs are given of the appearance of autocatalytic reactions on the oxidation of lignin at the level of one-electron transfer between the phenoxyl radicals being formed and the initial fragments and between chromophores in triplet electronically excited states and other fragments and of the development of concerted oxidation reactions through the appearance of active forms of oxygen, and vibrationally excited states. The results obtained indicate that on the oxidation of lignin in alkaline media a network of chemical reactions bearing the autocatalytic nature of chain processes with degenerate energy branching is formed.Siberian Scientific Research Institute of Cellulose and Board, Bratsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 426–433, May–June, 1988.     

Ion-exchange properties of ammoniated lignin

The oxidative ammonolysis of hydrolysis lignin from sunflower husks has given ion-exchange materials with amphoteric properties. The greatest total exchange capacity of the sample with respect to 0.1 N caustic soda solution amounted to 11.5 meq/g, and with respect to 0.1 N hydrochloric acid solution to 0.6 meq/g. The processes of ion exchange with heavy-metal cations are accompanied by complex formation. The bond of the metal cations with the lignin in the complexes is effected through nitrogen and the oxygen of a nonalcoholic group.Astrakhan Technical Institute of the Fish Industry and Agriculture. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 636–640, September–October, 1981.     

In situ DNA oxidative damage by electrochemically generated hydroxyl free radicals on a boron-doped diamond electrode

In situ DNA oxidative damage by electrochemically generated hydroxyl free radicals has been directly demonstrated on a boron-doped diamond electrode. The DNA-electrochemical biosensor incorporates immobilized double-stranded DNA (dsDNA) as molecular recognition element on the electrode surface, and measures in situ specific binding processes with dsDNA, as it is a complementary tool for the study of bimolecular interaction mechanisms of compounds binding to DNA and enabling the screening and evaluation of the effect caused to DNA by radicals and health hazardous compounds. Oxidants, particularly reactive oxygen species (ROS), play an important role in dsDNA oxidative damage which is strongly related to mutagenesis, carcinogenesis, autoimmune inflammatory, and neurodegenerative diseases. The hydroxyl radical is considered the main contributing ROS to endogenous oxidation of cellular dsDNA causing double-stranded and single-stranded breaks, free bases, and 8-oxoguanine occurrence. The dsDNA-electrochemical biosensor was used to study the interaction between dsDNA immobilized on a boron-doped diamond electrode surface and in situ electrochemically generate hydroxyl radicals. Non-denaturing agarose gel-electrophoresis of the dsDNA films on the electrode surface after interaction with the electrochemically generated hydroxyl radicals clearly showed the occurrence of in situ dsDNA oxidative damage. The importance of the dsDNA-electrochemical biosensor in the evaluation of the dsDNA-hydroxyl radical interactions is clearly demonstrated.