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Molecular Dynamics of Cation Hydration in the Presence of Carboxylated Molecules: Implications for Calcification

  • Biomineralization and Bioinspired Inorganic and Inorganic/Organic Materials
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Abstract

Biomolecules rich in aspartic acid (Asp) are known to play a role in biomineral morphology and polymorph selection, and have been shown to greatly enhance the growth kinetics of calcite. The mechanism by which these compounds favor calcification may be related to their effects upon cation solvation. Using molecular dynamics, we investigated the influence of small carboxylated molecules on the hydration states and water exchange rates of divalent cations. We show that the carboxylate moieties of Asp promote dehydration of Ca2+ and Sr2+ and that contact ion pair (CIP) formation is not required to disrupt the hydration of these cations. Ca2+- Asp and Sr2+ - Asp CIP formation decreases the total inner sphere coordination from an average of 8.0 and 8.4 in bulk water to 7.5 and 8.0, respectively. Water residence times estimated for Mg2+, Ca2+and Sr2+ follow the expected trend of decreasing residence time with increasing ionic radius. In the presence of Asp, both solvent-separated ion pair (SSIP) and CIP formation decrease the residence times of Ca2+and Sr2+ inner sphere water molecules. Comparable impacts on Mg2+ hydration are not observed. Mg2+ - Asp CIP formation is energetically unfavorable and Asp does not affect Mg2+ inner sphere water residence times.

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References

  1. A. M. Belcher, X. H. Wu, R. J. Christensen, P. K. Hansma, G. D. Stucky, D. E. Morse, Nature 381, 56 (1996).

    Article  CAS  Google Scholar 

  2. L. Addadi, S. Weiner, Proc Natl Acad Sci U S A 82, 4110 (1985).

    Article  CAS  Google Scholar 

  3. J. Aizenberg, L. Addadi, S. Weiner, G. Lambert, Adv. Mater. 8, 222 (1996).

    Article  CAS  Google Scholar 

  4. G. Falini, S. Albeck, S. Weiner, L. Addadi, Science 271, 67 (1996).

    Article  Google Scholar 

  5. S. Albeck, L. Addadi, S. Weiner, Connect. Tissue Res. 35, 365 (1996).

    Article  CAS  Google Scholar 

  6. S. Weiner, Troub, W., and Lowenstam, H.A., Biomineralization and Biological Metal Accumulation. P. a. E. W. d. J. Westbrowek, Ed., (Reidel Publishing Company, Dordrecht, 1983).

    Google Scholar 

  7. S. Elhadj, J. J. De Yoreo, J. R. Hoyer, P. M. Dove, Proc Natl Acad Sci U S A 103, 19237 (2006).

    Article  CAS  Google Scholar 

  8. A. E. Stephenson, J. J. DeYoreo, L. Wu, K. J. Wu, J. Hoyer, P. M. Dove, Science 322, 724 (2008).

    Article  CAS  Google Scholar 

  9. S. Chen, S. Yu, J. Jiang, F. Li, Y. Liu, Chem. Mater. 18, 115 (2006).

    Article  CAS  Google Scholar 

  10. S. Piana, F. Jones, J. D. Gale, J. Am. Chem. Soc. 128, 13568 (2006).

    Article  CAS  Google Scholar 

  11. M. Kowacz, C. Putnis, A. Putnis, Geochim Cosmochim Ac 71, 5168 (2007).

    Article  CAS  Google Scholar 

  12. M. Kowacz, A. Putnis, Geochim. Cosmochim. Acta 72, 4476 (2008).

    Article  CAS  Google Scholar 

  13. S. Kerisit, D. J. Cook, D. Spagnoli, S. C. Parker, J. Mater. Chem. 15, 1454 (2005).

    Article  CAS  Google Scholar 

  14. S. Piana, F. Jones, J. D. Gale, Crystengcomm 9, 1187 (2007).

    Article  CAS  Google Scholar 

  15. L. M. Hamm, A. F. Wallace, P. M. Dove, J Phys Chem B 114, 10488 (2010).

    Article  CAS  Google Scholar 

  16. L. M. Hamm, A. F. Wallace, P. M. Dove, J. Phys. Chem. B in prep, (2010).

  17. S. J. Plimpton, J. Comp. Phys. 117, 1 (1995).

    Article  CAS  Google Scholar 

  18. A. D. MacKerell, D. Bashford, M. Bellott, R. L. Dunbrack, J. D. Evanseck, M. J. Field, S. Fischer, J. Gao, H. Guo, S. Ha, D. Joseph-McCarthy, L. Kuchnir, K. Kuczera, F. T. K. Lau, C. Mattos, S. Michnick, T. Ngo, D. T. Nguyen, B. Prodhom, W. E. Reiher, B. Roux, M. Schlenkrich, J. C. Smith, R. Stote, J. Straub, M. Watanabe, J. Wiorkiewicz-Kuczera, D. Yin, M. Karplus, J. Phys. Chem. B 102, 3586 (1998).

    Article  CAS  Google Scholar 

  19. W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, M. L. Klein, J. Chem. Phys. 79, 926 (1983).

    Article  CAS  Google Scholar 

  20. J.-P. Ryckaert, G. Ciccotti, H. J. C. Berendsen, J. Comput. Phys. 23, 327 (1977).

    Article  CAS  Google Scholar 

  21. J. Aqvist, J. Phys. Chem. 94, 8021 (1990).

    Article  Google Scholar 

  22. C. S. Babu, C. Lim, J Phys Chem A 110, 691 (2006).

    Article  CAS  Google Scholar 

  23. A. R. Leach, Molecular modeling: principles and applications - 2nd edition. (Pearson Education Limited, Edinburgh Gate, 2001), pp. 580–585.

    Google Scholar 

  24. G. M. Torrie, J. P. Valleau, J. Comp. Phys. 23, 187 (1977).

    Article  Google Scholar 

  25. S. Kumar, D. Bouzida, R. H. Swendsen, P. A. Kollman, J. M. Rosenberg, J. Comp. Chem. 13, 1011 (1992).

    Article  CAS  Google Scholar 

  26. R. Rey, J. T. Hynes, J Phys-Condens Mat 8, 9411 (1996).

    Article  CAS  Google Scholar 

  27. R. W. Impey, P. A. Madden, I. R. Mcdonald, J Phys Chem-Us 87, 5071 (1983).

    Article  CAS  Google Scholar 

  28. R. Caminiti, G. Licheri, G. Piccaluga, G. Pinna, J. Appl. Cryst. 12, 34 (1972).

    Article  Google Scholar 

  29. A. Tongraar, B. M. Rode, Chem. Phys. Lett. 409, 304 (2005).

    Article  CAS  Google Scholar 

  30. F. Jalilehvand, D. Spångberg, P. Lindqvist-Reis, K. Hermansson, I. Persson, M. Sandström, J. Am. Chem. Soc. 123, 431 (2001).

    Article  CAS  Google Scholar 

  31. J. L. Fulton, S. M. Heald, J. Phys. Chem. A 107, 4688 (2003).

    Article  CAS  Google Scholar 

  32. J. P. Piquemal, L. Perera, G. A. Cisneros, P. Y. Ren, L. G. Pedersen, T. A. Darden, J Chem Phys 125, (2006).

  33. T. M. Seward, C. M. B. Henderson, J. M. Charnock, T. Driesner, Geochim. Cosmochim. Acta 63, 2409 (1999).

    Article  CAS  Google Scholar 

  34. R. H. Parkman, J. M. Charnock, F. R. Livens, D. J. Vaughan, Geochim Cosmochim Ac 62, 1481 (1998).

    Article  CAS  Google Scholar 

  35. R. Caminiti, A. Musinu, G. Paschina, G. Pinna, J. Appl. Cryst. 15, 482 (1982).

    Article  CAS  Google Scholar 

  36. J. P. Larentzos, L. J. Criscenti, J Phys Chem B 112, 14243 (2008).

    Article  CAS  Google Scholar 

  37. A. Bleuzen, P.-A. Pittet, L. Helm, A. E. Merbach, Magn. Reson. chem. 35, 765 (1997).

    Article  CAS  Google Scholar 

  38. Y. Marcus, Ion Solvation. (John Wiley & Sons, Chinchester, 1985).

    Google Scholar 

  39. S. Kerisit, S. C. Parker, J Am Chem Soc 126, 10152 (2004).

    Article  CAS  Google Scholar 

  40. R. W. Friddle, M. L. Weaver, S. R. Qiu, A. Wierzbicki, W. H. Casey, J. J. De Yoreo, P Natl Acad Sci USA 107, 11 (2010).

    Article  CAS  Google Scholar 

  41. D. Gebauer, A. Völkel, H. Cölfen, Science 322, 1819 (2008).

    Article  CAS  Google Scholar 

  42. E. M. Pouget, P. H. H. Bomans, J. A. C. M. Goos, P. M. Frederik, G. d. With, N. A. J. M. Sommerdijk, Science 323, 1455 (2009).

    Article  CAS  Google Scholar 

  43. D. Gebauer, A. Volkel, H. Colfen, Science 322, 1819 (2008).

    Article  CAS  Google Scholar 

  44. E. M. Pouget, P. H. Bomans, J. A. Goos, P. M. Frederik, G. de With, N. A. Sommerdijk, Science 323, 1455 (2009).

    Article  CAS  Google Scholar 

  45. D. Wang, A. F. Wallace, J. J. DeYoreo, P. M. Dove, Proc. Natl. Acad. Sci. USA 106, 21511 (2009).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Geosciences, Virginia Polytechnic Institute and State University, Blacksburg, VA, 24061, USA

    Laura M. Hamm & Patricia M. Dove

  2. Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    Adam F. Wallace

Authors
  1. Laura M. Hamm
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  2. Adam F. Wallace
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  3. Patricia M. Dove
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Hamm, L.M., Wallace, A.F. & Dove, P.M. Molecular Dynamics of Cation Hydration in the Presence of Carboxylated Molecules: Implications for Calcification. MRS Online Proceedings Library 1301, 51–61 (2011). https://doi.org/10.1557/opl.2011.197

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