Skip to main content
SpringerLink
Log in

Competition between counterions and active protein sites to bind bisquaternary ammonium groups. A combined mass spectrometry and quantum chemistry model study

  • Molecular Physics and Chemical Physics
  • Published:
The European Physical Journal D Aims and scope Submit manuscript

Abstract

A model study of the interaction between biologically active bisquaternary ammonium salts and their molecular targets in living systems is urgently needed to elucidate the molecular mechanisms involved in the interactions between these compounds. To address this need a combined experimental-computational study of the interaction of two tetramethylammonium cations (modeling two quaternary groups) with the chlorine anion and with the deprotonated 2,5-dihydroxybenzoic acid (modeling a carboxylic group and an aromatic ring of side radicals of proteins) has been performed. Fast atom bombardment mass spectrometry method and DFT/B3LYP/6-31++G** and MP2/6-31++G** calculations have been employed in the study. Stable noncovalent complexes with different ratios of the tetramethylammonium cations and chlorine anions or deprotonated 2,5-dihydroxybenzoic acid anions were registered in the mass spectra of tetramethylammonium chloride and 2,5-dihydroxybenzoic acid mixture. This finding shows that the organic and inorganic anions compete to bind tetramethylammonium in the studied system. The theoretically determined stabilities of the noncovalent complexes were compared with the relative stabilities evaluated from the mass spectrometric measurements. The results of the study allow us to elucidate the competing interactions that exist between quaternary groups with inorganic counterions or with active groups of molecular protein targets.

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

Access this article

Log in via an institution

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

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. V.A. Pashynskaya, M.V. Kosevich, A. Gomory, O.V. Vashchenko, L.N. Lisetski, Rapid Commun. Mass Spectrom. 16, 1706 (2002)

    Article  Google Scholar 

  2. V.A. Pashynska, M.V. Kosevich, H. Van den Heuvel, F. Cuyckens, M. Claeys, Biophysical Bulletin 14, 123 (2004)

    Google Scholar 

  3. V.A. Pashynska, M.V. Kosevich, A. Gomory, Z. Szilagyi, K. Vekey, S.G. Stepanian, Rapid Commun. Mass Spectrom. 19, 785 (2005)

    Article  Google Scholar 

  4. V.A. Pokrovsky, M.V. Kosevich, V.L. Osaulenko, V.V. Chagovets, V.A. Pashynska, V.S. Shelkovsky, V.A. Karachevtsev, A.Yu. Naumov, Mass-Spectrometria 2, 1 (2005)

    Google Scholar 

  5. V.A. Pashynska, M.V. Kosevich, S.G. Stepanian, Visnyk Problem Biology i Medicine 9, 118 (1999) (in Russian)

    Google Scholar 

  6. M.V. Kosevich, O.A. Boryak, V.V. Chagovets, V.A. Pashynska, V.V. Orlov, S.G. Stepanian, V.S. Shelkovsky, Rapid Commun. Mass Spectrom. 21, 1813 (2007)

    Article  Google Scholar 

  7. J.M. Llinares, D. Powell, K. Bowman-James, Coord. Chem. Rev. 240, 57 (2003)

    Google Scholar 

  8. J. De Mendoza, V. Alcázar, E. Botana, A. Galán, G. Lu, J.O. Magrans, M. Martín-Portugués, P. Prados, A. Salmerón, J. Sánchez-Quesada, C. Seel, M. Segura, Pure Appl. Chem. 69, 577 (1997)

    Article  Google Scholar 

  9. C.A. Hunter, Angew. Chem. Int. Ed. Engl. 40, 5310 (2004)

    Article  Google Scholar 

  10. V. Pashynska, M. Kosevich, S. Stepanian, L. Adamowicz, J. Mol. Struct. Theochem 815, 55 (2007)

    Article  Google Scholar 

  11. A.D. Becke, Phys. Rev. B 38, 3098 (1988)

    ADS  Google Scholar 

  12. C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37, 785 (1988)

    Article  ADS  Google Scholar 

  13. S.H. Vosko, L. Wilk, M. Nusair, Can. J. Phys. 58, 1200 (1980)

    Article  ADS  Google Scholar 

  14. S.F. Boys, F. Bernardi, Molec. Phys. 19, 553 (1970)

    Article  ADS  Google Scholar 

  15. M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, J.A. Montgomery, J.T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H.P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Pople, Gaussian 03, Revision E.01. (Gaussian Inc., Pittsburgh PA, 2003)

    Google Scholar 

  16. A.N. Barrett, G.C.K. Roberts, A.S.V. Burgen, G.M. Clore, Mol. Pharm. 24, 443 (1983)

    Google Scholar 

  17. L.F. Sukhodub, M.V. Kosevich, V.S. Shelkovsky, Yu.L. Volyansky, Antibiotiki i Chimiotherapia 34, 823 (1989) (in Russian)

    Google Scholar 

  18. L.F. Sukhodub, M.V. Kosevich, V.S. Shelkovsky, O.A. Boryak, Yu.L. Volyansky, V.I. Moleva, T.A. Chumachenko, Antibiotiki and Chimiotherapia 35, 10 (1989) (in Russian)

    Google Scholar 

  19. M.V. Kosevich, V.A. Pashinskaya, S.G. Stepanian, V.S. Shelkovsky, V.V. Orlov, Yu.P. Blagoy, Biophysical Bulletin 1, 22 (1999)

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine, Lenin Ave. 47, 61103, Kharkov, Ukraine

    V. Pashynska, O. Boryak, M. V. Kosevich & S. Stepanian

  2. Department of Chemistry, University of Arizona, 85721, Tucson, Arizona, USA

    L. Adamowicz

Authors
  1. V. Pashynska
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. O. Boryak
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. V. Kosevich
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. Stepanian
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. L. Adamowicz
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to V. Pashynska.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Pashynska, V., Boryak, O., Kosevich, M. et al. Competition between counterions and active protein sites to bind bisquaternary ammonium groups. A combined mass spectrometry and quantum chemistry model study. Eur. Phys. J. D 58, 287–296 (2010). https://doi.org/10.1140/epjd/e2010-00125-5

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1140/epjd/e2010-00125-5

Keywords

Search

Navigation