Skip to main content

Advertisement

Log in

New oxo-bridged peroxotungsten complexes containing biogenic co-ligand as potent inhibitors of alkaline phosphatase activity

  • Published:
Molecular and Cellular Biochemistry Aims and scope Submit manuscript

Abstract

Novel dinuclear peroxo complexes of tungsten with coordinated cystine of the type A2[W2O3(O2)4(cystine)].4H2O, A = Na (1) or K (2) have been synthesized from the reaction of A2WO4,cysteine and 30% H2O2at pH 2.5. The synthesized compounds were characterized by elemental analysis, spectral and physico-chemical methods. The two W(VI) centres with side-on bound peroxo groups of the dinuclear complex species are bridged by an oxo group and a cystine ligand, formed from the oxidation of cysteine. Cystine occurring as zwitterion binds the metal centers of the complex ion through O(carboxylate) atoms leading to hepta co-ordination around each W(VI). The compounds exhibit high stability toward decomposition in solution of acidic as well as physiological pH and serve as weak substrates to catalase, undergoing degradation in presence of the enzyme at a rate much slower relative to H2O2. The compounds efficiently oxidized GSH to GSSG, a reaction in which only two of the peroxide groups of the complex species were found to participate. The compounds induce strong inhibitory effect on alkaline phosphatase activity with a potency higher than that of the free cystine, tungstate, or peroxotungstate.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Johnson MK, Rees DC, Adams MWW: Tungstoenzymes. Chem Rev 96: 2817–2839, 1996

    Article  PubMed  CAS  Google Scholar 

  2. Enemark JH, Cooney JJA, Wang JJ, Holm RH: Synthetic analogues and reaction systems relevant to the molybdenum and tungsten oxotransferases. Chem Rev 104: 1175–1200, 2004

    Article  PubMed  CAS  Google Scholar 

  3. Louie AY, Meade TJ: Metal complexes as enzyme inhibitors. Chem Rev 99: 2711–2734, 1999

    Article  PubMed  CAS  Google Scholar 

  4. Moore PS, Jones CJ, Mahmood N, Evans IG, Goff M, Cooper R, Hay AJ: Anti- (human immunodeficiency virus) activity of polyoxotungstates and their inhibition of human immunodeficiency virus reverse transcriptase. Biochem J 307: 129–134, 1995

    Google Scholar 

  5. Stankiewiez PJ, Gresser MJ: Inhibition of phosphatase and sulfatase by transition state analogues. Biochemistry 27: 206–212, 1988

    Article  Google Scholar 

  6. Li J, Elberg G, Gefel D, Shechter Y: Permolybdate and Pertungstate- potent stimulators of insulin effects in rat adipocites: mechanism of action. Biochemistry 34: 6218–6225, 1995

    Article  PubMed  CAS  Google Scholar 

  7. Van-Etten RL, Waymack PP, Rehkop DM: Transition metal ion inhibition of enzyme catalysed phosphate ester displacement reactions. J Am Chem Soc 96: 6782–6785, 1974

    Article  CAS  Google Scholar 

  8. Soman G, Chang YC, Graves DJ: Effect of oxyanions of the early transition metals on rabbit skeletal muscle phosphorylase. Biochemistry 22: 4994–5000, 1983

    Article  PubMed  CAS  Google Scholar 

  9. Heo YS, Ryu JM, Park SM, Park JH, Lee HC, Hwang KY, Kim J: Structural basis for inhibition of protein tyrosine phosphatase by keggin compounds phosphomolybdate and phosphotungstate. Exp Mol Med 34: 211–223, 2002

    PubMed  CAS  Google Scholar 

  10. Crans DC, Smee JJ, Gaidamauskas E, Yang L: The chemistry and biochemistry of vanadium and biological activities exerted by vanadium compounds. Chem Rev 104: 849–902, 2004

    Google Scholar 

  11. Kustin K: Perspective on vanadium biochemistry. In: A.S. Tracy and D.C. Crans (eds). Vanadium Compounds Chemistry, Biochemistry, and Therapeutic Applications. Oxford University Press, New York, 1998, pp. 170–185

    Google Scholar 

  12. Crans DC: Peroxo hydroxylamido and acac derived vanadium complexes: Chemistry, biochemistry and insulinmimetic action of selected vanadium compounds. In: A.S. Tracy and D.C. Crans (eds). Vanadium Compounds Chemistry, Biochemistr, and Therapeutic Application. Oxford University Press, New York, 1998, pp. 82–103

    Google Scholar 

  13. Rehder D, Bashipoor M, Jantzen S, Schmidt H, Farahbakhsh M, Nekola H: Structural and functional models for biogenic vanadium compounds. In: A.S. Tracy and D.C. Crans (eds). Vanadium Compounds, Chemistry, Biochemistry, and Therapeutic Applications. Oxford University Press, New York, 1998, pp. 60–71

    Google Scholar 

  14. Shechter Y, Goldwaser I, Mironchik M, Fridkin M, Gefel D: Historic perspective and recent developments on the insulin like actions of vanadium; toward developing vanadium based drugs for diabetes. Coord Chem Rev 237: 3–11, 2003

    Article  CAS  Google Scholar 

  15. Djordjivic C, Vuletic N, Renslo ML, Puryear BC, Alimard R: Peroxo heteroligand vanadates(V): Synthesis, spectra-structure relationships, and stability toward decomposition. Mol Cell Biochem 153: 25–29, 1995

    Article  Google Scholar 

  16. Shaver A, Ng JB, Hall DA, Posner BI: The Chemistry of peroxovanadium compounds relevant to insulin mimesis. Mol Cell Biochem 153: 5–15, 1995

    Article  PubMed  CAS  Google Scholar 

  17. Kenneth S, Kirshenbaum KS, Sharpless KB: Improved procedure for the Tungstate catalysed epoxidation of α, β. unsaturated acids. J Org Chem 50: 1979–1982, 1985

    Google Scholar 

  18. Bortolini O, Furia FD, Modena G, Seraglia R: Metal catalysis in oxidation of peroxides. Sulfide oxidation and olefine epoxidation by dil H2O2,catalysed Mo and W derivatives under phase transfer conditions. J Org Chem 50: 2688–2690, 1985

    Google Scholar 

  19. Gresley NM, Griffith WP, Laemmel AC, Nogueira HIS, Parkin BC: Studies on polyoxo and polyperoxo metalates part 5: Peroxide catalised oxidation with heteropolyperoxo tungstates and molybdates. J Mol Catal A 117: 185–198, 1997

    Article  CAS  Google Scholar 

  20. Dickman MH, Pope MT: Peroxo and superopxo complexes of chromium, molybdenum and tungsten. Chem Rev 94: 569–584, 1994

    Article  CAS  Google Scholar 

  21. Campbell NJ, Dengel AC, Edwards CJ, Griffith WP: Studies on transition metal peroxo complexes. Part 8: The nature of peroxomolybdates and peroxotungstates in aqueous solution. JCS Dalton Trans: 1203–1207, 1989

  22. Dengel AC, Griffith WP, Powell RD, Skapski AC: Studies on transition metal peroxo complexes. Part 7: Mo(VI) and W(VI) carboxylato peroxo complexes and the Xray crystal strucures of K2[MoO(O2)2(glyc)]·2H2O. JCS Dalton Trans: 991–995, 1987

  23. Bhengu TT, Sanyal DK: Ligands effects on the stability of some Mo(VI) and W(VI) peroxo complexes. Part 2. Study of the thermal stability. Thermochimica Acta 397: 181–197, 2003

    CAS  Google Scholar 

  24. Piquemal JY, Halut S, Bregault JM: Novel Distorted pentagonal-pyramidal coordination of anionic oxodiperoxo molybdenum and tungsten complexes. Angew Chem Int Ed 37: 1146–1149, 1998

    Article  CAS  Google Scholar 

  25. Chakravorti MC, Ganguly S, Bhattacharjee M: First electrosynthesis of transition metal peroxocomplexes. Synthesis, characterisation and reactivity of molybdenum and tungsten heteroligand peroxocomplexes. Polyhedron 12: 55–58, 1993

    CAS  Google Scholar 

  26. Chaudhuri MK, Ghosh SK, Islam NS: First synthesis and structural assessment of alkali-metal triperoxo-vanadate(V).A[V(O2)3]. Inorg Chem 24: 2706–2707, 1985

    Article  CAS  Google Scholar 

  27. Jeffery GH, Basset J, Mendham J, Denny RC: Vogel's Textbook of Quantitative Inorganic Analysis Including Elementary Instrumentel Analysis, 4th edn, Longman Group Limited, London, pp. 486–487, 1978

  28. Ellmen GL: Tissue sulfhydryl groups. Arch Biochem Biophy 82: 70–77, 1959

    Article  Google Scholar 

  29. Nakamato K(ed).: Infrared and Raman Spectra of Inorganic and Coordination compounds. Part B,5th edn. J Wiley & Sons, New York, 1997, p. 210

  30. Nakamato K (ed).: Infrared and Raman Spectra of Inorganic and Coordination Compounds. Part B, 5th edn. J Wiley & Sons, New York, 1997, pp. 60, 71

    Google Scholar 

  31. Ravishankar HN, Rao AVS, Ramasarma T: Catalase degrades dipeoxovanadate and releases oxygen. Arch Biochem Biophys 321: 477–484, 1995

    Article  PubMed  CAS  Google Scholar 

  32. Chaudhuri MK, Paul PC: Complexes of peroxovanadates (V) containing chelated cystinate as the co-ligand: Synthesis and spectroscopic studies. Ind J Chem 31A: 466–468, 1992

    CAS  Google Scholar 

  33. Melby LR: Cysteine and Cysteine ester complexes with Mo(V) and Mo(VI). Inorg Chem 8: 349–353, 1969

    Article  CAS  Google Scholar 

  34. Chow ST, McAuliffe CA. In: Transition metal complexes containing tridentate amino acids. S. Lippared (ed). Progress in Inorganic Chemistry, Vol 19, Wiley Interscience, New York, 1975, 51–104

  35. Ravindranath V: Animal Models and Molecular Markers for Cerebral Ischemia Reperfusion Injury in Brain. In: L. Packer (ed). Methods in enzymology, Vol 233, Academic press Inc., 1994, pp. 613–617

  36. Shisheva A, Ikonomov O, Shechter Y: The protein tyrosine phosphatase inhibitor, pervanadate, is a powerful antidiabetic agent in streptozotocin-treated diabetic rats. Endocrinology 133: 507–510, 1994

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Nashreen s. Islam.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Hazarika, P., Kalita, D., Sarmah, S. et al. New oxo-bridged peroxotungsten complexes containing biogenic co-ligand as potent inhibitors of alkaline phosphatase activity. Mol Cell Biochem 284, 39–47 (2006). https://doi.org/10.1007/s11010-005-9011-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11010-005-9011-8

Keywords

Navigation