Abstract
Six alkylthiophenes, 2-hexadecyl-5-methylthiophene (I), 2-methyl-5-tridecylthiophene (II) and 2-butyl-5-tridecylthiophene (III), 2-(3,7-dimethyloctyl)-5-methylthiophene (IV), 2-methyl-5-(3,7,11,15-tetramethyl-hexadecyl)thiophene (V) and 2-ethyl-5-(3,7,11,15-tetramethylhexadecyl)thiophene (VI) were synthesized and used as substrates in biodegradation studies. The products of their aerobic metabolism by pure bacterial cultures were identified. In most cases, the long alkyl chains of these thiophenes were preferentially attacked and in pure cultures of alkane-degrading bacteria, the major metabolites that accumulated in the medium were 5-methyl-2-thiopheneacetic acid from (I), 5-methyl-2-thiophenecarboxylic acid from (II) and occasionally from (V), 5-butyl-2-thiophenecarboxylic acid from (III) and 5-ethyl-2-thiopheneacetic acid from (VI). These transformations are consistent with the metabolism of the alkyl side chains via the beta-oxidation pathway. In contrast, 5-(3,7-dimethyloctyl)-2-thiophenecarboxylic acid was produced from (IV). Because it was available in greatest supply, (I) was studied most thoroughly. It supported growth of the six n-alkanedegrading bacteria tested and (I) was degraded more quickly than pristance but not as quickly as n-hexadecance in mixtures of these three compounds. In the presence of Prudhoe Bay crude oil and a mixed culture of petroleum-degrading bacteria, the acid metabolites from (I), (II) and (III) underwent further biotransformations to products that were not detected by the analytical methods used. The addition of n-hexadecane to the mixed culture of petroleum-degrading bacteria also enhanced the further biotransformations of the metabolites from (I).
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References
Amphlett MJ & Callely AG (1969) The degradation of 2-thiophenecarboxylic acid by a Flavobacterium species. Biochem. J. 112: 12p
Blumer M & Sass J (1972) Oil pollution: persistence and degradation of spilled fuel oil. Science (Washington DC) 176: 1120–1122
Bohonos N, Chou T-W & Spanggord RJ (1977) Some observations on biodegradation of pollutants in aquatic systems. Jpn. J. Antibiot. 30 (suppl): 275–285
Cripps RE (1973) The microbial metabolism of thiophen-2-carboxylate. Biochem. J. 134: 353–366.
Cyr TD, Payzant JD, Montgomery DS & Strausz OP (1986) A homologous series of novel hopane sulfides in petroleum. Org. Geochem. 9: 139–143
Davis JB & Raymond RL (1961) Oxidation of alkyl-substituted cyclic hydrocarbons by Norcardia during growth on n-alkanes. Appl. Microbiol. 9: 383–388
Evans JS & Venables WA (1990) Degradation of thiophene-2-carboxylate, furan-2-carboxylate, pyrrole-2-carboxylate and other thiophene derivatives by the bacterium Vibrio YC1. Appl. Microbiol. Biotechnol. 32: 715–720
Fedorak PM (1990) Microbial metabolism of organosulfur compounds in petroleum. In: Orr WL & White CM (Eds) Geochemistry ofSulfur in Fossil Fuels (pp 93–112). ACS Books, Washington
Fedorak PM & Grbić-Galić D (1991) Aerobic microbial cometabolism of benzothiophene and 3-methylbenzothiophene. Appl. Environ. Microbiol. 57: 932–940
Fedorak PM, Payzant JD, Montgomery DS & Westlake DWS (1988) Microbial degradation of n-alkyl tetrahydrothiophenes found in petroleum. Appl. Environ. Microbiol. 54: 1243–1248
Fedorak PM & Westlake DWS (1981) Microbial degradation of aromatics and saturates in Prudhoe Bay crude oil as determined by glass capillary gas chromatography. Can. J. Microbiol. 27: 432–443
Fedorak PM & Westlake DWS (1983a) Microbial degradation of organic sulfur compounds in Prudhoe Bay crude oil. Can. J. Microbiol. 29: 291–296
Fedorak PM & Westlake DWS (1983b) Selective degradation of biphenyl and methylbiphenyls in crude oil by two strains of marine bacteria. Can. J. Microbiol. 29: 497–503
Fedorak PM & Westlake DWS (1986) Fungal metabolism of n-alkylbenzenes. Appl. Environ. Microbiol. 51: 435–437
Foght JM, Fedorak PM, Gray MR & Westlake DWS (1990a). Microbial desulfurization of liquid fossil fuels. In: Ehrlich HL Ed) Microbial Mineral Recovery (pp 379–407). MacGraw-Hill, New York
Foght JM, Fedorak PM & Westlake DWS (1990b) Mineralization of 14C-hexadecane and 14C-phenanthrene in crude oil: Specificity among bacterial isolates. Can. J. Microbiol. 36: 169–175
Furniss BS, Hannaford AJ, Smith PWG & Tatchell AR (1989) Vogel's Textbook of Practical Organic Chemistry, 5th edition. John Wiley & Sons, New York
Jobson A, McLaughlin M, Cook FD & Westlake DWS (1974) Effect of amendments on the microbial utilization of oil applied to soil. Appl. Microbiol. 27: 166–171
Kanagawa T & Kelly DP (1987) Degradation of substituted thiophenes by bacteria isolated from activated sludge. Microb. Ecol. 13: 47–57
Kargi F & Robinson JM (1984) Microbial oxidation of dibenzothiophene by the thermophilic organism Sulfolobus acidocaldarius. Biotechnol. Bioeng. 26: 687–690
Kodama K, Umehara K, Shimizu K, Nakatani S, Minoda Y & Yamada K (1973) Identification of microbial products from dibenzothiophene and its proposed oxidation pathway. Agric. Biol. Chem. 37: 45–50
Kohnen MEL, Sinninghe Damsté JS, Rijpstra WIC & de Leeuw JW (1990) Alkylthiophenes as sensitive indicators of palaeo-environmental changes: a study of a Cretaceous oil shale from Jordan. In: Orr WL & White CM (Eds) Geochemistry of Sulfur in Fossil Fuels (pp 444–485). ACS Books, Washington
Laborde AL & Gibson DT, (1977) Metabolism of dibenzothiophene by a Beijerinckia species. Appl. Environ. Microbiol. 34: 783–790
Mahler HR & Cordes EH (1966) Biological Chemistry. Harper and Row, New York
McClafferty FW (1980) Interpretation of Mass Spectra, 3rd edition (pp 64–67). University Science Books, Mill Valley California
McKenna EJ & Kallio RE (1971) Microbial metabolism of the isoprenoid alkane pristane. Proc. Nat. Acad. Sci. U.S.A. 68: 1552–1554
Mozingo R, Wolf DE, Harris SA & Folkers K (1943) Hydrogenolysis of sulfur compounds by Raney nickel catalyst. J. Am. Chem. Soc. 65: 1013–1016
Payzant JD, Montgomery DS & Strausz OP (1986) Sulfides in petroleum. Org. Geochem. 9: 357–369
Payzant JD, Montgomery DS & Strausz OP (1988) The identification of homologous series of benzo[b]thiophenes, thiophenes, thiolanes and thianes possessing a linear carbon framework in the pyrolysis oil of Athabasca asphaltene AOSTRA J. Res. 4: 117–131
Peakman TM & Kock-van Dalen AC (1990) Identification of alkylthiophenes occurring in the geosphere by synthesis of authentic standards. In: Orr WL & White CM (Eds) Geochemistry of Sulfur in Fossil Fuels (pp 397–416). ACS Books, Washington
Pirnik MP, Atlas RM & Bartha R (1974) Hydrocarbon metabolism by Brevibacterium erythrogenes: normal and branched alkanes. J. Bacteriol. 119: 868–878
Rall HT, Thompson CJ, Coleman HJ & Hopkins RL (1972) Sulfur Compounds in Crude Oil. U.S. Department of the Interior, Bureau of Mines, Bulletin 659
Ratledge C (1978) Degradation of aliphatic hydrocarbons. In: Watkinson RJ (Ed) Developments in Biodegradation of Hydrocarbons (pp 1–46). Applied Science Publishers, London
Saftić S, Fedorak PM & Andersson JT (1991) Aerobic microbial cometabolism of methylbenzothiophenes, 91st. Annual Meeting Am. Soc. Microbiol. (Dallas). Abstract Q81
Sagardia F., Rigau JJ, Martínez-Lahoz A, Fuentes F, López C & Flores W (1975) Degradation of benzothiophene and related compounds by a soil Pseudomonas in an oil-aqueous environment. Appl. Microbiol. 29: 722–725
Sariaslani FS, Harper DB & Higgins IJ (1974) Microbial degradation of hydrocarbons: catabolism of 1-phenyl-alkanes by Nocardia salmonicolor. Biochem. J. 140: 31–45
Silverstein RM & Bassler GC (1967) Spectrometric Identification of Organic Compounds, 2nd edition. John Wiley & Sons, New York
Sinninghe Damsté JS & de Leeuw JW (1990) Analysis, structure and geochemical significance of organically-bound sulphur in the geosphere: state of the art and future research. Org. Geochem. 16: 1077–1101
Sinninghe Damsté JS, ten Haven HL, de Leeuw JW & Schenck PA (1986) Organic geochemical studies of a Messinian evaporitic basin, northern Apennines (Italy). II. Isoprenoid and n-alkyl thiophenes and thiolanes. Org. Geochem. 10: 791–805
Sinninghe Damsté JS, de Leeuw JW, Kock-van Dalen AC, de Zeeuw MA, de Lange F, Rijpstra WIC & Schenck PA (1987) The occurrence and identification of series of organic sulphur compounds in oils and sediments. I. A study of Rozel Point oil (U.S.A.) Geochim. Cosmochim. Acta 51: 2369–2391
Sinninghe Damsté JS, Rijpstra WIC, de Leeuw JW & Schenck PA (1989) The occurrence and identification of series of organic sulphur compounds in oils and sediment extracts. II. Their presence in the samples from hypersaline and non-hypersaline depositional environments and possible application as source, maturity and palaeoenvironmental indicators. Geochim. Cosmochim. Acta. 53: 1323–1341
van Afferden M, Schacht S, Klein J & Trüper HG (1990) Degradation of dibenzothiophene by Brevibacterium sp. DO. Arch. Microbiol. 153: 324–328
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Fedorak, P.M., Peakman, T.M. Aerobic microbial metabolism of some alkylthiophenes found in petroleum. Biodegradation 2, 223–236 (1991). https://doi.org/10.1007/BF00114554
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DOI: https://doi.org/10.1007/BF00114554