Abstract
Enzymes of the p-cymene pathway in Pseudomonas putida strains cometabolized the intermediate analogue 4-trifluoromethyl(TFM)benzoate. Three products, 4-TFM-2,3-dihydro-2,3-dihydroxybenzoate, 4-TFM-2,3-dihydroxy-benzoate and 2-hydroxy-6-oxo-7,7,7-trifluorohepta-2,4-dienoate (7-TFHOD) were identified chemically and by spectroscopic proterties.
Certain TFM-substituted analogue metabolites of the p-cymene pathway were transformed at drastically reduced rates.
Hammett type analysis of ring cleavage reactions of 4-substituted 2,3-dihydroxybenzoates revealed the negative inductive and especially mesomeric effect of substituents to be rate determining. Whereas decarboxylation of 3-carboxy-7-TFHOD was not affected by fluorine substitution the subsequent hydrolysis of 7-TFHOD proceeded very slowly. The negative inductive effect of the TFM-group probably inhibited heterolysis of the carbon bond between C5 and C6 of 7-TFHOD.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
Abbreviations
- DHB:
-
1,2-Dihydroxy-2-hydrobenzoate
- DHC:
-
2,3-Dihydro-2,3-dihydroxybenzoate, this compound was termed DHC simply to distinguish it from the similar 1,2-dihydroxy-2-hydrobenzoate (DHB) as described in the preceeding paper (Engesser et al. 1988)
- HMS:
-
2-Hydroxymuconic semialdehyde
- HOD:
-
2-Hydroxy-6-oxohepta-2,4-dienoate
- 7-TFHOD:
-
2-Hydroxy-6-oxo-7,7,7-trifluorohepta-2,4-dienoate
- TFM:
-
Trifluoromethyl
References
Ali DA, Callely AG, Hayes M (1962) Ability of a vibrio grown on benzoate to oxidize para-fluorobenzoate. Nature 196:194–195
Bartels J, Knackmuss HJ, Reineke W (1984) Suicide inactivation of catechol-2,3-dioxygenase from Pseudomonas putida mt-2 by 3-halocatechols. Appl Environ Microbiol 47:500–505
Bialek J (1962) Decarboxylation of lutidinic and isocinchomeronic acids in ammonium bisulphate. Bull Acad Polon Science 10:625–627
Braendlin HP, McBee ET (1963) Effects of adjacent perfluoroalkyl groups on carbonyl reactivity. Adv Fluorine Chem 3:1–18
Clarke KF, Callely AG, Livingstone A, Fewson CA (1975) Metabolism of monofluorobenzoates by Acinetobacter calcoaceticus NCIB 8250: formation of monofluorocatechols. Biochim Biophys Acta 404:169–179
Dagley S (1978) Pathways for the utilization of organic growth substrates. In: Gunsalus LC (ed) The bacteria, vol VI. Academic Press, New York, pp 305–388
DeBoer TJ, Backer HJ (1954) A new method for the preparation of diazomethane. Rec Trav Chim 73:229–234
DeFrank JJ, Ribbons DW (1976) The p-cymene-pathway in Pseudomonas putida PL: isolation of a dihydrodiol accumulated by a mutant. Biochem Biophys Res Commun 70:1129–1195
DeFrank JJ, Ribbons DW (1977a) p-Cymene-pathway in Pseudomonas putida: initial reactions. J Bacteriol 129:1356–1364
DeFrank JJ, Ribbons DW (1977b) p-Cymene-pathway in Pseudomonas putida: ring cleavage of 2,3-dihydroxy-p-cumate and subsequent reactions. J Bacteriol 129:1365–1374
Dorn E, Knackmuss HJ (1978) Chemical structure and biodegradability of halogenated aromatic compounds: substituent effects on 1,2-dioxygenation of catechol. Biochem J 174:85–94
Duggleby CJ (1979) Studies on some enzymes involved in the metacleavage of catechol. Ph Thesis Dep Biochem Soil Sci Bangor, Wales
Duggleby CJ, Williams PA (1986) Purification and some properties of the 2-hydroxy-6-oxohepta-2,4-dienoate hydrolase (2-hydroxymuconic semialdehyde hydrolase) encoded by the TOL plasmid pWWO from Pseudomonas putida mt-2. J Gen Microbiol 132:717–726
Engesser KH, Cain RB, Knackmuss HJ (1988) Bacterial metabolism of side chain fluorinated aromatics: cometabolism of 3-trifluoromethyl(TFM)-benzoate by Pseudomonas putida (arvilla) mt-2 and Rhodococeus rubropertinctus N657. Arch Microbiol 149:188–197
Goldman P, Milne GWA, Pignataro MT (1967) Fluorine containing metabolites formed from 2-flurobenzoic acid by Pseudomonas species. Arch Biochem Biophys 118:178–184
Hamilton GA (1974) Chemical models and mechanisms for oxygenases. In: Hayaishi O (ed) Molecular mechanisms of oxygen activation. Academic Press, New York, pp 405–451
Harper DB, Blakley ER (1971) The metabolism of p-fluorobenzoic acid by a Pseudomonas sp. Can J Microbiol 17:1015–1023
Hartmann J, Reinecke W, Knackmuss HJ (1979) Metabolism of 3-chloro-,4-chloro- and 3,5-dichlorobenzoate by a pseudomonad. Appl. Environm Microbiol 37:421–428
Husain M, Entsch B, Ballou DP, Massey V, Chapman PJ (1980) Fluoride elimination from substrates in hydroxylation reactions catalyzed by p-hydroxybenzoate hydroxylase. J Biol Chem 255:4189–4197
Husted DR, Ahlbrecht AH (1952) The chemistry of perfluoro acids and their derivates. J Am Chem Soc 74:5422–5426
Iwaki M, Nozaki M (1982) Immobilization of metapyrocatechase and its properties in comparison with the soluble enzyme. J Biochem 91:1549–1553
Jungclaus GA, Lopez-Avila V, Hites RA (1978) Organic compounds in an industrial wastewater: a case study of their environmental impact. Environm Sci Techn 12:88–96
Klĉka GM, Gibson DT (1981) Inhibition of catechol 2,3-dioxygenase from Pseudomonas putida by 3-chlorocatechol. Appl Environ Microbiol 41:1159–1165
Lombardo P (1979) FDA's chemical contaminants program: the search for the unrecognized pollutant. In: Nicholson WJ, Moore JA (eds) Health effects of halogenated aromatic hydrocarbons, vol 320. New York Acad of Science, New York, pp 673–677
Maier EJ, Fritschi G, Kussmaul H (1978) Identifizierung von Fluorkohlenwasserstoffen im Main mittels Gaschromatographie-Massenspektrometric. Vom Wasser 51:227–234
Meyer R (1883) Untersuchungen über Hydroxylierung durch direkte Oxydation. Annal Chem 219:234–250
Milne GWA, Goldman P, Holtzman JL (1968) The metabolism of 2-fluorobenzoic acid. II. Studies with 18O2. J Biol Chem 243:5374–5376
MS-Data-Centre (1974) Eight peak index of mass spectra, 2nd edn. Mass Spectrometry Data Centre, Reading, p 274
Norman ROC, Taylor R (1965) Electrophilic substitution in benzenoid compounds. Elsevier, Amsterdam
Que Jr L, Lipscomb JD, Münck E, Wood JM (1977) Protocatechuate 3,4-dioxygenase inhibitor studies and mechanistic implications. Biochim Biophys Acta 485:60–74
Reineke W, Knackmuss HJ (1978a) Chemical structure and biodegradability of halogenates aromatic compounds. Substituent effects on 1,2-dioxygenation of benzoic acids. Biochim Biophys Acta 542:412–423
Reineke W, Knackmuss HJ (1978b) Chemical structure and biodegradability of halogenated compounds. Substituent effects on dehydrogenation of 3,5-cyclohexadiene-1,2-diol-1-carboxylic acid. Biochim Biophys Acta 542:424–429
Shaw DA, Borkenhagen LF, Talalay P (1965) Enzymatic oxidation of steroids by cell-free extracts of Pseudomonas testosteroni: isolation of cleavage products of ring a. Proc Nat Acad Sci 54:837–844
Smith A, Trauter EK, Cain RB (1968) The utilization of some halogenated aromatic acids by Nocardia. Biochem J 106:203–209
Stenhagen E, Abrahamsson S, McLafferty FW (1974) Registry of mass spectral data, vol 2. John Wiley, New York, p 937
Wessely F, Benedikt K, Benger H, Friedrich G, Prillinger F (1950) Zur Kenntnis der Carboxylierung von Phenolen. Monatsh Chem 81:1071–1091
Wigmore GJ, Ribbons DW (1980) p-Cymene pathway in Pseudomonas putida: defective mutants by using selective enrichment of halogenated substrate analogs. J Bacteriol 143:816–824
Wigmore GJ, Ribbons DW (1981) Selective enrichment of Pseudomonas spp defective in catabolism after exposure to halogenated substrates. J Bacteriol 146:920–927
Williams DH, Fleming J (1975) Spektroskopische Methoden der Strukturaufklärung. Thieme, Stuttgart, pp 162–216
Author information
Authors and Affiliations
Additional information
This work was supported, in part, by the Gesellschaft für Strahlen- und Umweltforschung, Neuherberg/München, FRG
Rights and permissions
About this article
Cite this article
Engesser, K.H., Rubio, M.A. & Ribbons, D.W. Bacterial metabolism of side chain fluorinated aromatics: cometabolism of 4-trifluoromethyl(TFM)-benzoate by 4-isopropylbenzoate grown Pseudomonas putida JT strains. Arch. Microbiol. 149, 198–206 (1988). https://doi.org/10.1007/BF00422005
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00422005