The thiocarbamate-inducible Rhodococcus enzyme ThcF as a member of the family of α/β hydrolases with haloperoxidative side activity

Purified thiocarbamate-inducible ThcF of Rhodococcus erythropolis NI86/21, overexpressed in Escherichia coli, displayed several characteristics of the HASH family of enzymes that groups prokaryotic proteins of the α/β hydrolase superfamily possessing serine-dependent hydrolase and/or haloperoxidase activity. Kinetic analysis of bromination and ester hydrolysis revealed a low affinity of ThcF for model substrates. Sulfoxidation of thiocarbamates was demonstrated but probably represents a side activity due to peroxoacid generation by the enzyme. The thcF-linked thcG gene, encoding a LAL-type regulator, triggers expression of thcF in Rhodococcus. The tandem gene organization thcG-thcF is conserved in the thiocarbamate-degrading strain Rhodococcus sp. B30. It is proposed that HASH enzymes may be involved in the metabolism of plant-derived compounds.

[1]  Z. Shao,et al.  Characterization of the expression of the thcB gene, coding for a pesticide-degrading cytochrome P-450 in Rhodococcus strains , 1996, Applied and environmental microbiology.

[2]  V. Burd,et al.  Phosphatase activity of non‐heme chloroperoxidase from the bacterium Serratia marcescens , 2003, FEBS letters.

[3]  Yves Van de Peer,et al.  TREECON for Windows: a software package for the construction and drawing of evolutionary trees for the Microsoft Windows environment , 1994, Comput. Appl. Biosci..

[4]  A. Sakimae,et al.  Nucleotide sequence of the gene for a thermostable esterase from Pseudomonas putida MR-2068. , 1995, Bioscience, biotechnology, and biochemistry.

[5]  H. Sobek,et al.  The metal-ion-free oxidoreductase from Streptomyces aureofaciens has an α/β hydrolase fold , 1994, Nature Structural Biology.

[6]  K. van Pée,et al.  Chloroperoxidase from Streptomyces lividans: isolation and characterization of the enzyme and the corresponding gene , 1994, Journal of bacteriology.

[7]  G. Schoofs,et al.  Thiocarbamate herbicide-inducible nonheme haloperoxidase of Rhodococcus erythropolis NI86/21 , 1997, Applied and environmental microbiology.

[8]  E. Sakuradani,et al.  Role of Acinetobacter calcoaceticus 3,4-dihydrocoumarin hydrolase in oxidative stress defence against peroxoacids. , 2003, European journal of biochemistry.

[9]  A. Schrijver,et al.  Degradation of Pesticides by Actinomycetes , 1999 .

[10]  T. Dairi,et al.  Cloning and biochemical characterization of Co(2+)-activated bromoperoxidase-esterase (perhydrolase) from Pseudomonas putida IF-3 strain. , 2001, Biochimica et biophysica acta.

[11]  J. Vanderleyden,et al.  A single cytochrome P-450 system is involved in degradation of the herbicides EPTC (S-ethyl dipropylthiocarbamate) and atrazine by Rhodococcus sp. strain NI86/21 , 1995, Applied and environmental microbiology.

[12]  K. van Pée,et al.  Purification, characterization and comparison of two non-haem bromoperoxidases from Streptomyces aureofaciens ATCC 10762. , 1991, Journal of general microbiology.

[13]  Jürgen Eck,et al.  Screening for novel enzymes for biocatalytic processes: accessing the metagenome as a resource of novel functional sequence space. , 2002, Current opinion in biotechnology.

[14]  I. Pelletier,et al.  A bacterial esterase is homologous with non-haem haloperoxidases and displays brominating activity. , 1995, Microbiology.

[15]  K. van Pée,et al.  Antifungal and peroxidative activities of nonheme chloroperoxidase in relation to transgenic plant protection. , 2000, Journal of agricultural and food chemistry.

[16]  K. Pée Microbial biosynthesis of halometabolites , 2001, Archives of Microbiology.

[17]  Z. Shao,et al.  Cloning of the genes for degradation of the herbicides EPTC (S-ethyl dipropylthiocarbamate) and atrazine from Rhodococcus sp. strain TE1 , 1995, Applied and environmental microbiology.

[18]  G. Schoofs,et al.  Degradation of the thiocarbamate herbicide EPTC (S-ethyl dipropylcarbamothioate) and biosafening by Rhodococcus sp. strain NI86/21 involve an inducible cytochrome P-450 system and aldehyde dehydrogenase , 1995, Journal of bacteriology.

[19]  A. Schrijver,et al.  A subfamily of MalT-related ATP-dependent regulators in the LuxR family. , 1999 .

[20]  K. Pée,et al.  BIOSYNTHESIS OF HALOGENATED METABOLITES BY BACTERIA , 1996 .

[21]  G. Schoofs,et al.  Characterization of the Rhodococcus sp. NI86/21 gene encoding alcohol: N,N′-dimethyl-4-nitrosoaniline oxidoreductase inducible by atrazine and thiocarbamate herbicides , 1995, Archives of Microbiology.

[22]  I. Pelletier,et al.  Cloning of a second non-haem bromoperoxidase gene from Streptomyces aureofaciens ATCC 10762: sequence analysis, expression in Streptomyces lividans and enzyme purification. , 1994, Microbiology.

[23]  T. Cleveland,et al.  Inhibition of fungal growth in planta and in vitro by transgenic tobacco expressing a bacterial nonheme chloroperoxidase gene , 2000, Plant Cell Reports.

[24]  K. van Pée,et al.  Evaluation of peracid formation as the basis for resistance to infection in plants transformed with haloperoxidase. , 2002, Journal of agricultural and food chemistry.

[25]  Assaf Na,et al.  Spheroplast formation and plasmid isolation from Rhodococcus spp. , 1993 .

[26]  M. Kataoka,et al.  3,4-Dihydrocoumarin hydrolase with haloperoxidase activity from Acinetobacter calcoaceticus F46. , 2000, European journal of biochemistry.

[27]  M. Picard,et al.  Metal-Free Bacterial Haloperoxidases as Unusual Hydrolases: Activation of H2O2 by the Formation of Peracetic Acid†‡ , 1997 .

[28]  H. Spaink,et al.  Infection-blocking genes of a symbiotic Rhizobium leguminosarum strain that are involved in temperature-dependent protein secretion. , 2003, Molecular plant-microbe interactions : MPMI.

[29]  T. Dairi,et al.  Reaction mechanism of the Co2+-activated multifunctional bromoperoxidase-esterase from Pseudomonas putida IF-3. , 2002, Archives of Biochemistry and Biophysics.

[30]  I. Pelletier,et al.  A catalytic triad is required by the non-heme haloperoxidases to perform halogenation. , 1995, Biochimica et biophysica acta.

[31]  I. Pelletier,et al.  Molecular cloning and sequencing of a non-haem bromoperoxidase gene from Streptomyces aureofaciens ATCC 10762. , 1992, Journal of general microbiology.

[32]  S. Lam,et al.  The non-haem chloroperoxidase from Pseudomonas fluorescens and its relationship to pyrrolnitrin biosynthesis. , 1996, Microbiology.

[33]  Robert H. White,et al.  The genome of M. acetivorans reveals extensive metabolic and physiological diversity. , 2002, Genome research.

[34]  R. Ankumah,et al.  Enhanced Degradation of S-EthylN,N-Dipropylcarbamothioate in Soil and by an Isolated Soil Microorganism , 1990 .

[35]  K. van Pée,et al.  Chloroperoxidase-encoding gene from Pseudomonas pyrrocinia: sequence, expression in heterologous hosts, and purification of the enzyme. , 1993, Gene.

[36]  H. Hecht,et al.  Structural investigation of the cofactor-free chloroperoxidases. , 1998, Journal of molecular biology.

[37]  M. Kataoka,et al.  Enzymatic preparation of D-β-acetylthioisobutyric acid and cetraxate hydrochloride using a stereo- and/or regioselective hydrolase, 3,4-dihydrocoumarin hydrolase from Acinetobacter calcoaceticus , 2002, Applied Microbiology and Biotechnology.