Enols of aldehydes in the peroxidase/oxidase-promoted generation of excited triplet species.

作者: Waldemar Adam , Wilhelm J. Baader , Giuseppe Cilento

DOI: 10.1016/0304-4165(86)90023-1

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摘要: General (acid and base) or specific (fluoride ion) catalysis generates the enol of isobutanal propanal from corresponding trimethylsilyl ethers. The enols are directly rapidly oxidized by peroxidase (acting as an oxidase) to triplet acetone acetaldehyde, respectively, formic acid. Due faster rate reaction absence quenching excess aldehyde, excited carbonyl emits more strongly than when aldehyde itself is substrate. With both emission pure phosphorescence. Both acetaldehyde generated within enzyme, shown different D- L-tryptophan, somewhat protected oxygen quenching, attested very fact that phosphorescence observed. use precursors substrates opens wide possibilities for photochemical investigations in light over a much broader range experimental conditions.

参考文章(19)
W J Baader, C Bohne, G Cilento, H B Dunford, Peroxidase-catalyzed formation of triplet acetone and chemiluminescence from isobutyraldehyde and molecular oxygen. Journal of Biological Chemistry. ,vol. 260, pp. 10217- 10225 ,(1985) , 10.1016/S0021-9258(17)39234-7
Herbert O. House, Leonard J. Czuba, Martin Gall, Hugh D. Olmstead, Chemistry of carbanions. XVIII. Preparation of trimethylsilyl enol ethers Journal of Organic Chemistry. ,vol. 34, pp. 2324- 2336 ,(1969) , 10.1021/JO01260A018
Herbert O. House, Martin Gall, Hugh D. Olmstead, Chemistry of carbanions. XIX. Alkylation of enolates from unsymmetrical ketones Journal of Organic Chemistry. ,vol. 36, pp. 2361- 2371 ,(1971) , 10.1021/JO00815A037
Edy I. Rivas, Alejandro Paladini, Giuseppe Cilento, PHOTOCHEMICAL‐LIKE DESTRUCTION OF TRYPTOPHAN IN SERUM ALBUMINS INDUCED BY ENZYME‐GENERATED TRIPLET SPECIES Photochemistry and Photobiology. ,vol. 40, pp. 565- 568 ,(1984) , 10.1111/J.1751-1097.1984.TB05342.X
H.Brian Dunford, Wilhelm J. Baader, Cornelia Bohne, Giuseppe Cilento, On the Mechanism of Peroxidase-Catalyzed Chemiluminescence From Isobutyraldehyde Biochemical and Biophysical Research Communications. ,vol. 122, pp. 28- 32 ,(1984) , 10.1016/0006-291X(84)90434-0
Raymond F. Borkman, David R. Kearns, Electronic‐Relaxation Processes in Acetone Journal of Chemical Physics. ,vol. 44, pp. 945- 949 ,(1966) , 10.1063/1.1726846
Giuseppe Cilento, Generation of electronically excited triplet species in biochemical systems Pure and Applied Chemistry. ,vol. 56, pp. 1179- 1190 ,(1984) , 10.1351/PAC198456091179
W. J. Leigh, J. C. Scaiano, Photochemistry of acetone in surfactant solutions Journal of the American Chemical Society. ,vol. 105, pp. 5652- 5657 ,(1983) , 10.1021/JA00355A022
Hugo Gallardo, Lidia A. Guillo, Nelson Durán, Giuseppe Cilento, Catalysis of the peroxidase-mediated oxidation of aldehydes by enolphosphates Biochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology. ,vol. 789, pp. 57- 62 ,(1984) , 10.1016/0167-4838(84)90060-8
Marcela Haun, Nelson Durán, Ohara Augusto, Giuseppe Cilento, Model studies of the α-peroxidase system: Formation of an electronically excited product☆ Archives of Biochemistry and Biophysics. ,vol. 200, pp. 245- 252 ,(1980) , 10.1016/0003-9861(80)90351-3