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Titolo:
Isotope-effect profiles in the oxidative N-demethylation of N,N-dimethylanilines catalysed by lignin peroxidase and a chemical model
Autore:
Baciocchi, E; Gerini, MF; Lanzalunga, O; Lapi, A; Lo Piparo, MG; Mancinelli, S;
Indirizzi:
Univ La Sapienza, Dipartimento Chim, I-00185 Rome, Italy Univ La SapienzaRome Italy I-00185 partimento Chim, I-00185 Rome, Italy Univ La Sapienza, Dipartimento Chim, I-00185 Rome, Italy Univ La SapienzaRome Italy I-00185 partimento Chim, I-00185 Rome, Italy Univ La Sapienza, CNR, Ctr Studio Meccanismi Reaz, I-00185 Rome, Italy Univ La Sapienza Rome Italy I-00185 Meccanismi Reaz, I-00185 Rome, Italy
Titolo Testata:
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
fascicolo: 12, , anno: 2001,
pagine: 2305 - 2310
SICI:
1434-193X(200106):12<2305:IPITON>2.0.ZU;2-G
Fonte:
ISI
Lingua:
ENG
Soggetto:
BASIDIOMYCETE PHANEROCHAETE-CHRYSOSPORIUM; BOND-DISSOCIATION ENERGIES; VERATRYL ALCOHOL; CRYSTAL-STRUCTURE; DEGRADING ENZYME; RADICAL CATIONS; COMPOUND-I; REDOX; BIODEGRADATION; DEALKYLATION;
Keywords:
enzyme catalysis; oxidations; porphyrinoids; oxidoreductases; anilines;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
42
Recensione:
Indirizzi per estratti:
Indirizzo: Baciocchi, E Univ La Sapienza, Dipartimento Chim, P A Moro 5, I-00185 Rome, Italy Univ La Sapienza P A Moro 5 Rome Italy I-00185 5 Rome, Italy
Citazione:
E. Baciocchi et al., "Isotope-effect profiles in the oxidative N-demethylation of N,N-dimethylanilines catalysed by lignin peroxidase and a chemical model", EUR J ORG C, (12), 2001, pp. 2305-2310

Abstract

Lignin peroxidase catalyses the oxidative N-demethylation of ring-substituted N,N-dimethylanilines by an electron-transfer mechanism whereby an anilinium radical cation is formed which is then deprotonated by the enzyme. Information on the nature of the basic centre which deprotonates the radical cation has been obtained by determining the KDIE profile (plot of k(H)/k(D),vs, the pK(a) of the aniline radical cations) for a number of ring-substituted N, N-bis(dideuteriomethyl) anilines. From the bell-shaped curve it hasbeen estimated that the pK(a) of the proton-abstracting base is about 7. Interestingly, almost the same value has been obtained when the same type ofstudy has been carried out using a water-soluble model compound: 5,10,15,20-tetraphenyl-21H,23H-porphine-p,p',p",p"'-tetrasulfonic acid iron(III) chloride. This is a strong indication that the radical cation is deprotonated by the same species in the enzymatic and in the chemical reactions. It is suggested that this species is the reduced iron-oxo complex.

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Documento generato il 01/04/20 alle ore 17:16:32