An experimental investigation of the tautomers of adenine

Bergmann, Ernst D.; Weiler‐Feilchenfeld, Hannah; Neiman, Z.

doi:10.1039/j29700001334

Cited by 20 publications

(16 citation statements)

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“…5 The first experimental investigation of aminoimino tautomerism of adenine was performed in 1970. 6 The obtained results were in agreement with previous theoretical predictions formulated by Pullman et al 7 Modern computing methods and experimental techniques allow one to elucidate the molecular structure in greater detail and to perform a deeper analysis of tautomeric mixtures. Recently 23 prototropic tautomers (nine amino and fourteen imino forms) were investigated.…”

Section: Introductionsupporting

confidence: 89%

Effect of H-bonding and complexation with metal ions on the π-electron structure of adenine tautomers

2014

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Influence of H-bonding and interactions with metals via complexation (probed by HF, F(-), Li(+) and Na(+)) on structural and π-electronic changes in four of the most stable amino adenine tautomers has been studied in the gas phase using the B3LYP/6-311++G(2d,2p) computational level. It has been found that the presence of the amino group in adenine increases its energetic sensitivity to structural changes caused by tautomeric effects as compared to its analogue deprived of this group (purine). Furthermore, its shape depends not only on tautomerism but also on intermolecular interactions. The observed variability of its pyramidalizations caused by H-bonding indicates the dramatic changes of electron donating/accepting properties of -NH2 as a substituent, which results in a variation of aromaticity of particular rings in adenine tautomers. Bifurcated coordination of metal cations by two nitrogen atoms of adenine is also an important factor influencing aromaticity. The overall range of H-bond strengths is between -4.64 and -26.39 kcal mol(-1), whereas energies for Li(+) and Na(+) complexes are in the ranges -41.45 to -67.50 and -25.04 to -51.39 kcal mol(-1), respectively. However, the highest aromaticity changes, expressed by the HOMA index, have been found to be about 24% of the HOMA scale for all types of complexes depending on the location of the intermolecular interaction.

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Section: Introductionsupporting

confidence: 89%

Effect of H-bonding and complexation with metal ions on the π-electron structure of adenine tautomers

2014

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“…A comparison of the experimental dipole moments of methyl and benzyl adenine derivatives, measured in dioxane, with calculated dipole moments indicates that the most stable tautomer of adenine is the N(9)H form. 35 In NMR studies of adenine in Me2SO it is found that adenine exists in an amino N(9)H structure. 36 Results of magnetic circular dichromism studies of adenine,12 the N(9)H and N(7)H tautomers occur in approximately equal quantities.…”

Section: Resultsmentioning

confidence: 99%

Ultraviolet photoelectron studies of the ground-state electronic structure and gas-phase tautomerism of purine and adenine

Lin¹,

Cheng²,

Peng³

et al. 1980

J. Am. Chem. Soc.

173

120

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“…This dependence on solvent polarity has been explained by the 7-H tautomer having a substantially larger dipole moment than the 9-H tautomer. 19,44 Naturally, the amount of published material is less exhaustive for 2-aminopurine. Very recent calculations show that the 9-H tautomer has about 18 kJ/mol lower enthalpy of formation than the 7-H tautomer of 2-aminopurine in the gas phase.…”

Section: Discussionmentioning

confidence: 99%

Electronic Transition Moments of 2-Aminopurine

1997

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The electronic spectrum of the unnatural nucleic acid base 2-aminopurine is important in order to understand the spectroscopy and photophysics of the normal DNA bases. Knowledge of transition moment directions and effective absorption components is also a prerequisite for the interpretation of emission spectra of 2-aminopurine incorporated into DNA as a probe of nucleic acid base motion or excitation energy transfer processes. Using linear dichroism, fluorescence anisotropy, and ordinary and magnetic circular dichroism techniques, the near-UV spectrum of 2-aminopurine is resolved into contributions from five electronic transitions. Four moderately strong π f π* transitions (I, III, IV, and V) are observed, polarized at +53°(I), -72°(III), -77°(IV), and +57°or -67°(V) relative to the short molecular axis. In addition, one weak n f π* transition (II) polarized perpendicular to the molecular plane has been identified. Semiempirical INDO/S calculations support these assignments.

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An experimental investigation of the tautomers of adenine

Cited by 20 publications

References 0 publications

Effect of H-bonding and complexation with metal ions on the π-electron structure of adenine tautomers

Effect of H-bonding and complexation with metal ions on the π-electron structure of adenine tautomers

Ultraviolet photoelectron studies of the ground-state electronic structure and gas-phase tautomerism of purine and adenine

Electronic Transition Moments of 2-Aminopurine

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