Biopolym. Cell. 1997; 13(3):185-190.
Structure and Function of Biopolymers
To the question of tautomerism of nucleic acid bases
1Boldeskul A. I., 1Sukhodub L. F.
- Institute of Applied Physics, NAS of Ukraine
58, Petropavlivska Str., Sumy, Ukraine, 40030
Abstract
The tautomerism of nucleic acids bases was investigated by semi-empirical method MNDO/H with optimization of all structural parameters. Utilization of MNDO method in similar investigations is fully justified, since the obtained calculated data are in good agreement with the experimental ones. Besides «classical» keto-amine tautomcric forms of the bases, there is the possibility of realization of isolated and paired liquid enole or imine forms in gaseous phase. Enole tautomer of guanine, for example, appeared 7.2 kcal/mol more preferable that keto-amine form, and O(4) enole tautomer of thy mine is 0.6 kcal/mol more preferable than dike-toform. The conclusion was drawn on the bases of proton-acceptor ability of nitrous bases that for the molecules of nitrous bases there is t/ie preference of thermodynamic control over the protonation of nucteophilic centres represented by O(2) cytozine, O(4) thymine, N(l), N(3) adenine and N(7) guanine
Full text: (PDF, in Russian)
References
[1]
Danilov VI, Kventsel GF. Electronic submission to the theory of point mutations. Kiev: Naukova Dumka, 1971; 83 p.
[2]
Topal MD, Fresco JR. Complementary base pairing and the origin of substitution mutations. Nature. 1976;263(5575):285-9.
[3]
Brown T, Hunter WN, Leonard GA. Mismatches in DNA duplexes. Chem. Brit. 1993; 29(6): 484-8.
[4]
Florian J, Hrouda V, Hobza P. Proton Transfer in the Adenine-Thymine Base Pair. J Am Chem Soc. 1994;116(4):1457–60.
[5]
Sheina GG, Radchenko ED, Stepanian SG, Blagoi YuP. Prototropic tautomerizm of nucleic acid purine bases. Stud biophys. 1986; 114(1-3):123-31
[6]
Radchenko ED, Plokhotnichenko AM, GG Sheina, Blagoy YuP. Infrared and electron-oscillation spectra of adenine and substitutes in argon matrix. Biofizika. 1984; 29(4):553-9.
[7]
Czerminski R, Szczepaniak K, Person WB, Kwiatkowski JS. Intermolecular interactions and tautomerism of nucleic acid bases and their analogues. J Mol Struct. 1990;237:151–63.
[8]
Pivovarov VB, Reva ID, Stepan'yan SG, Sheina GG, Blagoi YuP. Study of the imino form of 1-methyladenine in argon cryomatrix and in solution by IR-spectroscopy. Biofizika. 1995; 40(6):1189-201
[9]
Grebneva EA. The role of hydrogen bonds in the genetic mutations formation. Khim Fizika. 1993; 12(7): 1027-31.
[10]
Dewar MJ. New ideas about enzyme reactions. Enzyme. 1986;36(1-2):8-20.
[11]
Dewar MJS, Zoebisch EG, Healy EF, Stewart JJP. Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model. J Am Chem Soc. 1985;107(13):3902–9.
[12]
Clark T, A Handbook of Computational Chemistry: A Practical Guide to Chemical Structure and Energy Calculations 1985. Wiley 352 p.
[13]
Dewar MJS, Thiel W. Ground states of molecules. 38. The MNDO method. Approximations and parameters. J Am Chem Soc. 1977;99(15):4899–907.
[14]
Govorun DM, Mischuk YaR, Kondratyuk IV, Zheltovs'kyi MV. About nonplanarity h-bonded pairs of complementary DNA. Proc. I Ukr. Pol. Symposium. by hydrogen bonding. Odessa, 1992: 26.
[15]
Govorun DM, Mischuk YaR, Kondratyuk IV, Zheltovs'kyi MV. Dynamic stereo isomerism of Watson-Crick nucleotide base pairs. Dopovidi Nats Akad Nauk Ukrainy. 1995;(11):121-3.
[16]
Govorun DN, Danchuk VD, Kondratyuk IV et al. Study of structural and dynamic features of the nucleotide bases and some methyl derivatives by AMI. Proc. Dokl. VII Conf. on the spectroscopy of biopolymers. Kharkiv, 1991: 63.
[17]
Govorun DN, Danchuk VD, Mishchuk YaR, Kondratyuk IV, Radomsky NF, Zheltovsky NV. Mirror symmetrical conformational states of canonical nucleic acid bases. Doklady Akad Nauk Ukrainy. 1992; (2):66-9.
[18]
Sponer J, Hobza P. Nonplanar geometries of DNA bases. Ab initio second-order Moeller-Plesset study. J Phys Chem. 1994;98(12):3161–4.
[19]
Govorun DM, Kondratyuk IV, Mishchuk YaR, Zheltovskyi MV. The nonequavalence of amine hydrogens in canonical nucleotide bases. Dopovidi Nats Akad Nauk Ukrainy. 1995; (8):130-2.
[20]
Hoogsteen K. The crystal and molecular structure of a hydrogen-bonded complex between 1-methylthymine and 9-methyladenine. Acta Cryst. 1963;16(9):907–16.
[21]
Barker DL, Marsh RE. The crystal structure of cytosine. Acta Cryst. 1964;17(12):1581–7.
[22]
Sukhorukov BI, Gukovskaia AS, Sukhoruchkina LV, Lavrenova GI. [Optical properties and molecular structure of nucleic acids and their components. V. Spectrophotometric determination of thermodynamic parameters for protolytic reactions of cytosine and its N- and O-methyl derivatives]. Biofizika. 1972;17(1):5-11.
[23]
Vo?tiuk AA, Blizniuk AA. [Effect of protonation of nucleic acid bases on the energy of formation of the Watson-Crick pairs]. Mol Biol (Mosk). 1988;22(4):1080-6.
[24]
Sukhodub LF, Aksenov SA, Boldeskul AI. [Mass spectrometric and quantum chemical study of dimeric associates of nucleosides]. Biofizika. 1995;40(3):506-12.
[25]
Krugliak IuA, Danilov VI, Shramko OV et al. [Scheme pairing of nucleic acid bases]. Biofizika. 1965. 10(3): 399-403.
[26]
Shramko OV, Danilov VI, Krugliak IuA. [The pi-electron structure of DNA rare pairs of bases and the mechanism of spontaneous mutations connected with tautomeria of bases]. Biofizika. 1965;10(4):561-6.
[27]
Mirck J, Sygula A. MNDO study of the tautomers of nucleic bases. J Mol Struct. TEOCHEM. 1987; 86: 275-292.
[28]
Sheina GG, Stepanian SG, Radchenko ED, Blagoi YP. IR spectra of guanine and hypoxanthine isolated molecules. J Mol Struct. 1987;158:275–92.
[29]
Radchenko Ed, Plokhotnichenko AM, Sheina GG, Blagoy YuP. Infra-red spectra of cytosine and its deravatives in argon matrix at low temperature. Biofizika. 1983;28(4):559-63.
[30]
Sukhodub LF, Aksenov SA, Boldeskul AI. [Mass spectrometric and quantum chemical study of dimeric associates of nucleosides]. Biofizika. 1995;40(3):506-12.
