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Quantum chemical calculations of the dissociation constants pK a for l-Ala-C60H (an amino acid derivative of fullerene) in water

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Abstract

The absolute pK a values of the α-COOH, α-NH, and CH groups of the fullerene derivative l-Ala-C60H in water were calculated by quantum chemical methods. The gas phase basicities were calculated by the DFT method B3LYP/6-31G(d)//B3LYP/6-311++G(2d,p). The Gibbs free energies of solvation were calculated at the Hartree-Fock and B3LYP levels in combination with the polarizable continuum model. The stabilities of the l-Ala-C60H isomers and the lowest-energy conformers for neutral and anionic states were determined at the B3LYP/6-31G(d) level. The CH group at fullerene in l-Ala-C60H is less basic in the gas phase than the CH group in C60H2 and than the COOH group in l-Ala-C60H and AcOH. The calculated pK a values of the dissociating groups in water increase in the order: NH2 +(COOH-CH(Me)-NH 2 +-C60H) < COOH (COOH-CH(Me)-NH-C60H) < COOH (AcOH) < CH (COOH-CH(Me)-NH-C60 H) < CH (C60 H 2) < NH3 + (Me-NH 3 +). The amino group in l-Ala-C60H is electrically neutral, while the carboxy group is negatively charged at physiological pH values. The COOH group in l-Ala-C60H is more acidic (pK a = 4.2) than the CH group at fullerene (pK a = 5.8). The results of the calculations agree with the experimental data on the chemical reactivities of these compounds.

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References

  1. Y. Z. An, J. L. Anderson, Y. Rubin, J. Org. Chem., 1993, 58, 4799.

    Article  CAS  Google Scholar 

  2. A. Skiebe, A. Hirsch, J. Chem. Soc., Chem. Commun., 1994, 335.

    Google Scholar 

  3. V. S. Romanova, V. A. Tsyryapkin, Yu. I. Lyakhovetskii, Z. N. Parnes, M. E. Vol’pin, Russ. Chem. Bull. (Engl. Transl.), 1994, 53, 1090 [Izv. Akad. Nauk, Ser. Khim., 1994, 1154].

    Article  Google Scholar 

  4. M. E. Vol’pin, V. S. Romanova, Z. N. Parnes, Mol. Cryst. Liq. Cryst. Sci. Technol., Sect. C, 1996, 7, 53.

    Google Scholar 

  5. M. E. Vol’pin, Z. N. Parnes, V. S. Romanova, Russ. Chem. Bull. (Engl. Transl.), 1998, 57, 1021 [Izv. Akad. Nauk, Ser. Khim., 1998, 1050].

    Article  Google Scholar 

  6. A. Bianco, T. Da Ros, M. Prato, C. Toniolo, J. Pept. Sci., 2001, 7, 208.

    Article  CAS  Google Scholar 

  7. N. E. Fedorova, S. M. Adueva, A. A. Medzhidova, V. S. Romanova, Z. N. Parnes, G. A. Galegov, A. A. Kushch, Vopr. Virusol. [Problems of Virology], 2002, 30 (in Russian).

    Google Scholar 

  8. R. A. Kotelnikova, G. N. Bogdanov, E. C. Frog, A. I. Kotelnikov, V. N. Shtolko, V. S. Romanova, S. M. Andreev, A. A. Kushch, N. E. Fedorova, A. A. Medzhidova, G. G. Miller, J. Nanopart. Res., 2003, 5, 561.

    Article  CAS  Google Scholar 

  9. G. G. Miller, V. S. Romanova, L. N. Pokidysheva, I. V. Titova, E. N. Kaliberda, L. D. Rumsh, O. I. Andreeva, N. P. Rybalkin, Antibiot. Khimioter. [Antibiotics and Chemotherapy], 2004, 49, 3 (in Russian).

    CAS  Google Scholar 

  10. V. V. Grigoriev, L. N. Petrova, T. A. Ivanova, R. A. Kotelnikova, G. N. Bogdanov, D. A. Poletaeva, I. I. Faingold, D. V. Mishchenko, V. S. Romanova, A. I. Kotelnikov, S. O. Bachurin, Biochemistry, 2011, 38, 125 [Izv. Akad. Nauk, Ser. Biol., 2011, 163].

    CAS  Google Scholar 

  11. M. D. Liptak, K. C. Gross, P. G. Seybold, S. Feldgus, G. C. Shields, J. Am. Chem. Soc., 2002, 124, 6421.

    Article  CAS  Google Scholar 

  12. J. J. Klicic, R. A. Friesner, S.-Y. Liu, W. C. Guida, J. Phys. Chem. A, 2002, 106, 1327.

    Article  CAS  Google Scholar 

  13. J. Ho, M. L. Coote, Theor. Chem. Acc., 2010, 125, 3.

    Article  CAS  Google Scholar 

  14. V. B. Luzhkov, Russ. Chem. Bull. (Int. Ed.), 2014, 561 [Izv. Akad. Nauk, Ser. Khim., 2014, 63, 561].

    Google Scholar 

  15. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., 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 D.01, Gaussian, Inc., Wallingford (CT), 2004.

    Google Scholar 

  16. M. Cossi, G. Scalmani, N. Rega, V. Barone, J. Chem. Phys., 2002, 117, 43.

    Article  CAS  Google Scholar 

  17. V. Barone, M. Cossi, J. Tomasi, J. Chem. Phys., 1997, 107, 3210.

    Article  CAS  Google Scholar 

  18. M. D. Tissandier, K. A. Cowen, W. Y. Feng, E. Gundlach, M. H. Cohen, A. D. Earhart, J. V. Coe, T. R. Tuttle, Jr., J. Phys. Chem. A, 1998, 102, 7787.

    Article  CAS  Google Scholar 

  19. T. Yu. Dolinina, V. B. Luzhkov, Russ. Chem. Bull. (Int. Ed.), 2012, 61, 1631 [Izv. Akad. Nauk, Ser. Khim., 2012, 1614].

    Article  CAS  Google Scholar 

  20. V. R. Williams, H. B. Williams, Basic Physical Chemistry for the Life Sciences, W. H. Freeman and Co., San Francisco, 1973.

    Google Scholar 

  21. J. R. Pliego, Jr., J. M. Riveros, Phys. Chem. Chem. Phys., 2002, 4, 1622.

    Article  CAS  Google Scholar 

  22. A. I. Kotelnikov, V. S. Romanova, G. N. Bogdanov, N. P. Konovalova, O. I. Pisarenko, R. A. Kotelnikova, I. I. Faingold, E. S. Frog, Yu. N. Bubnov, M. I. Davydov, S. M. Aldoshin, RF Pat. 2462473 (granted on June 19, 2007).

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation

    V. B. Luzhkov & A. I. Kotelnikov

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    V. S. Romanova

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  1. V. B. Luzhkov
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  2. V. S. Romanova
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  3. A. I. Kotelnikov
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Correspondence to V. B. Luzhkov.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 0567–0571, March, 2014.

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Luzhkov, V.B., Romanova, V.S. & Kotelnikov, A.I. Quantum chemical calculations of the dissociation constants pK a for l-Ala-C60H (an amino acid derivative of fullerene) in water. Russ Chem Bull 63, 567–571 (2014). https://doi.org/10.1007/s11172-014-0474-1

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  • DOI: https://doi.org/10.1007/s11172-014-0474-1

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