Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pK(a) = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k(2) = 1.8-2.7 x 10(9) M-1 s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation. of the reduced acceptor (methyl viologen radical cation, MV+center dot), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2center dot)(OH)CH2-(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled with the low rates of beta-fragmentation of the same species have an important bearing in the context of the photoyellowing of lignin containing pulps and papers.

Fabbri, C., Bietti, M., Lanzalunga, O. (2005). Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers, 70(7), 2720-2728 [10.1021/jo047826u].

Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers

BIETTI, MASSIMO;
2005-01-01

Abstract

Ketyl radicals with lignin related structures have been generated by means of radiation chemical and photochemical techniques. In the former studies ketyl radicals are produced by reaction of alpha-carbonyl-beta-aryl ether lignin models with the solvated electron produced by pulse radiolysis of an aqueous solution at pH 6.0. The UV-vis spectra of ketyl radicals are characterized by three main absorption bands. The shape and position of these bands slightly change when the spectra are recorded in alkaline solution (pH 11.0) being now assigned to the ketyl radical anions and a pK(a) = 9.5 is determined for the 1-(3,4,5-trimethoxyphenyl)-2-phenoxyethanol-1-yl radical. Decay rates of ketyl radicals are found to be dose dependent and, at low doses, lie in the range (1.7-2.7) x 10(3) s(-1). In the presence of oxygen a fast decay of the ketyl radicals is observed (k(2) = 1.8-2.7 x 10(9) M-1 s(-1)) that is accompanied by the formation of stable products, i.e., the starting ketones. In the photochemical studies ketyl radicals have been produced by charge-transfer (CT) photoactivation of the electron donor-acceptor salts of methyl viologen (MV2+) with alpha-hydroxy-alpha-phenoxymethyl-aryl acetates. This process leads to the instantaneous formation. of the reduced acceptor (methyl viologen radical cation, MV+center dot), as is clearly shown in a laser flash photolysis experiment by the two absorption bands centered at 390 and 605 nm, and an acyloxyl radical [ArC(CO2center dot)(OH)CH2-(OC6H5)], which undergoes a very fast decarboxylation with formation of the ketyl radicals. Steady-state photoirradiation of the CT ion pairs indicates that 1-aryl-2-phenoxyethanones are formed as primary photoproducts by oxidation of ketyl radicals by MV2+ (under argon) or by molecular oxygen. Small amounts of acetophenones are formed by further photolysis of 1-aryl-2-phenoxyethanones and not by beta-fragmentation of the ketyl radicals. The high reactivity of ketyl radicals with oxygen coupled with the low rates of beta-fragmentation of the same species have an important bearing in the context of the photoyellowing of lignin containing pulps and papers.
2005
Pubblicato
Rilevanza internazionale
Articolo
Sì, ma tipo non specificato
Settore CHIM/06 - CHIMICA ORGANICA
English
Con Impact Factor ISI
Carboxylation; Charge transfer; Chemical activation; Light absorption; Photolysis; Radiolysis; Structure (composition); Ultraviolet spectroscopy; Ketyl radicals; Photoactivation; Photoyellowing; Lignin; acetic acid derivative; acetophenone derivative; alkali; argon; cation; ethane; inorganic salt; ion; ketone; lignin; oxygen; paraquat; radical; absorption; article; chemical analysis; chemical reaction; chemical structure; color; decarboxylation; electricity; electron; experiment; irradiation; molecule; paper; pH; photoactivation; photochemistry; photolysis; photooxidation; reaction analysis; recording; spectrum; steady state; structure analysis; ultraviolet spectroscopy; Activation; Charge Transfer; Decarboxylation; Light Absorption; Lignins; Photolysis; Radiolysis; Structures
Fabbri, C., Bietti, M., Lanzalunga, O. (2005). Generation and reactivity of ketyl radicals with lignin related structures. On the importance of the ketyl pathway in the photoyellowing of lignin containing pulps and papers, 70(7), 2720-2728 [10.1021/jo047826u].
Fabbri, C; Bietti, M; Lanzalunga, O
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/38261
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