Skip to main content

Microbial hydroxylation of imidacloprid for the synthesis of highly insecticidal olefin imidacloprid

Applied Microbiology and Biotechnology volume 71, pages 927–934 (2006)Cite this article

Abstract

Microorganisms that bring about the aerobic transformation of imidacloprid (IMI) were isolated and screened, and the microbial regio- and stereoselective hydroxylation of IMI was studied. Some bacteria and fungi transformed IMI to 5-hydroxyl IMI. Bacterium Stenotrophomonas maltophilia CGMCC 1.1788 resting cells transformed IMI into R-5-hydroxyl IMI at the highest conversion rate. The enzyme catalyzed the stereoselective hydroxylation at position C12 of IMI in the imidazolidine ring. Under acidic conditions, 5-hydroxyl IMI was converted into olefin IMI in high molar conversion yield. The olefin IMI exhibited about 19 and 2.2 times more insecticidal efficacy than IMI against horsebean aphid imago and nymph, respectively, and about 1.4 times more active than IMI against brown planthopper imago. The transformation rate of IMI by resting cells of S. maltophilia CGMCC 1.1788 was promoted significantly by some carbohydrates and organic acids. The reaction medium with 5% sucrose resulted in 8.3 times greater biotransformation yield as compared with that without sucrose.

This is a preview of subscription content, access via your institution.

Access options

Buy single article

Instant access to the full article PDF.

43,34 €

Price includes VAT (Finland)
Tax calculation will be finalised during checkout.

Fig. 1
Fig. 2
Fig. 3
Fig. 4

References

  • Asperger O, Steinbrenner H, Lehmann A, Petsch M, Griengl H (1999) Induction and functional role of cytochromes P450 in the filamentous fungi Mortierella alpine ATCC 8979 and Cunninghamella blakesleeana DSM 1906 during hydroxylation of cycloalkylbenzoxazoles. Appl Microbiol Biotechnol 51:516–522

    Article  CAS  Google Scholar 

  • Bradford M (1976) A rapid and sensitive method for the quantification of microgram quantities of protein utilizing the principle of protein dye binding. Anal Biochem 72:248–254

    Article  CAS  Google Scholar 

  • Caroline C (2001) Imidacloprid. J Pestic Reform 21:15–21

    Google Scholar 

  • Claude B, Davin-Regli A, De Micco P (1995) A simple method for selective isolation of Stenotrophomonas maltophilia from environmental samples. Appl Environ Microb 61:1653–1654

    Article  Google Scholar 

  • Holland HL (2000) Stereoselective hydroxylation reactions. In: Patel RN (ed) Stereoselective biocatalysis. Marcel Dekker, New York, pp 131–152

    Chapter  Google Scholar 

  • Hurek T, Wagner B, Reinhold-Hurek B (1997) Identification of N2-fixing plant- and fungus-associated Azoarcus species by PCR-based genomic fingerprints. Appl Environ Microbiol 65:4331–4339

    Article  Google Scholar 

  • Krohn J, Hellpointner E (2002) Environmental fate of imidacloprid. Pflanzenschutz-Nachr Bayer 55: 3–26 (special edition)

    CAS  Google Scholar 

  • Lewis D, Hlavica P (2000) Interactions between redox partners in various cytochrome P450 systems: functional and structural aspects. Biochim Biophys Acta 1460:353–374

    Article  CAS  Google Scholar 

  • Liu W, Zheng W, Gan J (2002) Competitive sorption between imidacloprid and imidacloprid-urea on soil clay minerals and humic acids. J Agric Food Chem 50:6823–6827

    Article  CAS  Google Scholar 

  • Nagasawa T, Hurh B, Yamamne T (1994) Production of 6-hydroxynicotinic acid from nicotinic acid by resting cells of Pseudomonas fluorescens TN5. Biosci Biotechnol Biochem 58:665–668

    Article  CAS  Google Scholar 

  • Nauen R, Tietjen K, Wagner K, Elbert A (1998) Efficacy of plant metabolites of imidacloprid against Myzus persicae and Aphis gossypii (Homoptera: Aphididae). Pestic Sci 52:53–57

    Article  CAS  Google Scholar 

  • Nauen R, Rechmann U, Armborst S, Stupp HP, Elbert A (1999) Whitefly-active metabolites of imidacloprid: biological efficacy and translocation in cotton plants. Pestic Sci 55:265–271

    Article  CAS  Google Scholar 

  • Nauen R, Ebbinghaus-Kintscher U, Schmuck R (2001) Toxicity and nicotinic acetylcholine receptor interaction of imidacloprid and its metabolites in Apis mellifera (Hymenoptera: Apidae). Pest Manag Sci 57:577–586

    Article  CAS  Google Scholar 

  • Rouchaud J, Gustin F, Wauters A (1994) Soil biodegradation and leaf transfer of insecticide imidacloprid applied in seed dressing in sugar beet crops. Bull Environ Contam Toxicol 53:344–350

    Article  CAS  Google Scholar 

  • Rouchaud J, Gustin F, Wauters A (1996) Imidacloprid insecticide metabolism in sugar beet field crops. Bull Environ Contam Toxicol 56:29–36

    Article  CAS  Google Scholar 

  • Sabate J, Grifoll M, Vinas M, Solanas A (1999) Isolation and characterization of a 2-methylphenanthrene utilizing bacterium: identification of ring cleavage metabolites. Appl Microbiol Biotechnol 52:704–712

    Article  CAS  Google Scholar 

  • Sarkar MA, Sankhajit R, Kole R, Chowdhury A (2001) Persistence and metabolism of imidacloprid in different soils of West Bengal. Pest Manag Sci 57:598–602

    Article  CAS  Google Scholar 

  • Schoning R (2001) Analytical method for the determination of residues of imidacloprid, NTN 33893-5-hydroxyl, and NTN 33893-olefin by HPLC with electrospray MS/MS-detection in plant and other materials: honey, nectar, bees, wax, corn (pollen, leaves), rape (pollen, flowers, leaves), sunflowers (pollen, flowers, leaves), tree (leaves, flowers), horse chestnuts. Pflanzenschutz-Nachr Bayer 54:413–452

    CAS  Google Scholar 

  • Schulz-Jander D, Casida J (2002) Imidacloprid insecticide metabolism: human cytochrome P450 isozymes differ in selectivity for imidazolidine oxidation versus nitroimine reduction. Toxicol Lett 132:65–70

    Article  CAS  Google Scholar 

  • Suchail S, Debrauwer L, Belzunces L (2004) Metabolism of imidacloprid in Apis mellifera. Pest Manag Sci 60:291–296

    Article  CAS  Google Scholar 

  • Uchida A, Yoshida T, Ogawa M, Nagasawa T (2003) Regioselective hydroxylation of quinolinic acid, lutidinic acid and isocinchomeronic acid by resting cells of pyridine dicarboxylic acid-degrading microorganisms. Appl Microbiol Biotechnol 62:337–341

    Article  CAS  Google Scholar 

  • Wahl P, Walser-Volken P, Laumen K, Kittelmann M, Ghisalba O (1999) Microbial production, purification, and characterization of (S)-specific N-acetyl-2-amino-1-phenyl-4-pentene amidohydrolase from Rhodococcus globerulus K1/1. Appl Microbiol Biotechnol 53:12–18

    Article  CAS  Google Scholar 

  • Woo PCY, Lau SKP, Fung AMY, Chiu SK, Yung RWH, Yuen KY (2003) Gemella Bacteraemia characterised by 16S ribosomal RNA gene sequencing. J Clin Pathol 56: 690–693

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We are thankful for support from the 10th Five Years Project for the National Key Technologies R&D Program (2004BA308A22-12) and the Jiangsu Academic Natural Science Foundation (04KJB180071). We especially thank Dr. Ji-Hua Liu of China Pharmaceutical University for conducting M.S. studies and Dr. Jia-Hong Zhou for conducting NMR studies. We sincerely acknowledge Dr. Bing-Xiang Wang for analytical assistance.

Author information

Affiliations

  1. Jiangsu Key Lab for Bioresource Technology, Key Lab for Microbial Technology in College of Life Science, Nanjing Normal University, Nanjing, 210097, PR China

    Yi-jun Dai, Sheng Yuan, Feng Ge & Ting Chen

  2. Jiangsu Pesticide Research Institute, Nanjing, 210036, PR China

    Shang-cheng Xu & Jue-ping Ni

Authors
  1. Yi-jun Dai
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Sheng Yuan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Feng Ge
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ting Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Shang-cheng Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Jue-ping Ni
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Sheng Yuan.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Dai, Yj., Yuan, S., Ge, F. et al. Microbial hydroxylation of imidacloprid for the synthesis of highly insecticidal olefin imidacloprid. Appl Microbiol Biotechnol 71, 927–934 (2006). https://doi.org/10.1007/s00253-005-0223-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00253-005-0223-3

Keywords

  • Imidacloprid
  • Transformation Activity
  • Acetamiprid
  • Brown Planthopper
  • Biotransformation Product