Relationship between RNA/DNA ratio, growth rate and accumulation of selenium in the cells of wheat leaves under the influence of minerals analcime and trepel.

We studied specific effects of different doses of natural minerals--analcime (An) and trepel (Tr)--on the growth rate, selenium (Se) content and functional activity of the genome of wheat leaves measured by the RNA/DNA ratio. Our results show that under the influence of An and Tr, especially at low doses (25 mg/100 g sand), there is a significant increase in the content of Se, increased growth rate of leaves of wheat seedlings and decreased RNA/DNA ratio. We have found significant correlations between studied parameters.

Homodimers of cytosine and 1-methylcytosine. A DFT study of geometry, relative stability and H-NMR shifts in gas-phase and selected solvents.

Dimers of cytosine and its N¹-methylated counterpart were investigated in gas-phase and in various solvents including chloroform, dimethylsulfoxide, and water. The studies were performed at DFT/M06-2X/6-31+G(d,p) level of theory. Relative stabilities of tautomers of cytosine solvated explicitly by a small number of solvent molecules were evaluated.

Tautomeric equilibrium of uracil and thymine in model protein-nucleic acid contacts. Spectroscopic and quantum chemical approach.

This work deals with tautomeric transformations of uracil (Ura) and thymine (Thy) in their model complexes with the deprotonated carboxylic group. Essential changes in the UV spectra of the bases upon their interaction with NaAc, vanishing signals of both imino protons in (1)H NMR spectra, and a perceptible decrease in intensity of both IR bands, related to the stretching vibrations nu(C=O) of the carbonyl groups, imply involvement of enolic tautomers. Results of quantum chemical calculations of the double complexes of the Ura(Thy) tautomers with CH(3)COO(-) at the MP2/6-311++G(2df,pd)//B3LYP/6-311++G(d,p) level of theory proved to be incompatible with the spectral features: despite the fact that the complexes of the enolic tautomers are much closer in energy to the diketo ones as compared to isolated tautomers, the energy gap between them is such that in tautomeric equilibrium dominate diketo forms.

ATR-IR spectroscopy as applied to nucleic acid films.

For the first time the ATR technique was applied to obtain IR absorption spectra of DNA and RNA dry films. There was worked out procedure of the nucleic acid removal from germanium plate, which obviously was a main obstacle to application of ATR-IR spectroscopy to nucleic acids. This technique of IR spectroscopy was applied to confirmation of RNA tropism of aurin tricarboxylic acid observed by molecular biological methods.

Specific interaction of isocytosine and amino acid carboxylic group shifts the base tautomeric equilibrium.

By 1H NMR, UV and IR spectroscopies in anhydrous DMSO and quantum-chemical calculations by MNDO/H in vacuum specific interactions of isocytosine with neutral and deprotonated carboxylic groups of amino acids were investigated. In vacuum interaction with carboxylate ion provokes in isoCyt transition from the ground-state enolic form to the high energy N3H-keto tautomer. In DMSO keto tautomer N3H of isoCyt is stabilized but interactions with carboxylate ion essentially shifts equilibrium to enolic form.

UV spectra of adenine methyl and glycosyl derivatives and their transformation induced by amino acid carboxylic groups.

UV absorption spectra of adenine, adenosine and their methyl derivatives were studied in dimethylsuloxide (DMSO). Considerable changes in UV spectra of adenine under methylation at the 1 and 3 positions, and adenosine under methylation at the 1 position attested the essential structural reconstruction of adenine purine ring. Ade and m6Ade were shown to form complexes with deprotonated carboxylic group of amino acids (carboxylate-ion) through two H-bonds involving amino group and N7H imino group, tautomeric transition N9H-->N7H being initiated namely by interaction with carboxylate-ion.

Recognition modes of hypoxanthine, xanthine and their derivatives by amino acid carboxylic group: UV spectroscopic and quantum chemical data.

UV absorption spectra of Hyp, Xan, their nucleosides and methyl derivatives were studied in anhydrous dimethylsuloxide and the changes in these spectra on the interactions with neutral and deprotonated carboxylic groups of amino acids were traced. By the semiempirical quantum-chemical method MNDO/H it was shown, that interaction with carboxylate-ion fixes Hyp as the rare N7H enolic tautomer and converts Xan into its N9H diketo tautomeric form with a probable admixture of the N7H O6-enolic form. Significant changes in the UV spectra of Xan, m3Xan, m9Xan and X under interaction with carboxylate-ion are determined by essential contribution to complex formation of proton transfer from bases to ligands, m9Xan and X proving to be slightly protonated even by the solvent.

UV spectra of guanine methyl and glycosyl derivatives and their transformations induced by interactions with amino acids via carboxylic group in dimethylsulfoxide.

UV absorption spectra of guanine derivatives m9Gua, m(2)2,9Gua, m1Gua, m(2)1,7Gua, m3Gua, G, dG, m1G, m2G, m7G, as well as guanine analogue isoGua were studied in anhydrous dimethylsulfoxide (DMSO). Changes in UV absorption spectra of guanine derivatives in the presence of amino acid derivatives with neutral carboxylic group (ac-Asp, ac-Glu, ac-Gly, ac-Asp-OMe) or deprotonated carboxylic group (NaAc, f-Gly-ONa) were investigated and interpreted. The m1Gua and m7Gua derivatives were shown to exist as the N9H tautomers in anhydrous DMSO.

Specific interactions of deprotonated carboxylic group with uracil and thymine provoke diketo-->keto-enol tautomeric transition in bases.

The 1H NMR and MNDO/H calculation data combined indicate the uracil and thymine tautomeric transitions from the ground diketo tautomeric state to the high-energy keto-enol one stimulated by specific interaction with carboxylate ion in anhydrous DMSO, which is blocked by base methylation at the 1 or 3 positions.