Synthetic spectroscopic models related to coenzymes and base pairs. II. Evidence for intramolecular base-base interactions in dinucleotide analogs

Browne, Douglas T.; Eisinger, Joseph; Leonard, Nelson J.

doi:10.1021/ja01028a023

Cited by 260 publications

(103 citation statements)

References 7 publications

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“…In the case of A3, both destabilizing factors, electronic and steric, cooperate. These results are in agreement with experimental observations, i.e., in basic conditions the reaction with a variety of reagents proceeds on N9 [20,24,84,85].…”

Section: The Energy Diagram Of Adenine Reactions With Hsupporting

confidence: 92%

Nucleophilic properties of purine bases: inherent reactivity versus reaction conditions

Stachowicz‐Kuśnierz

Korchowiec

2015

Struct Chem

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In the present study, nucleophilic properties of adenine and guanine are examined by means of density functional theory. H? is used as a model electrophile. Two modes of H ? attack on the bases are considered: on the neutral molecule and on the anion. Solvent effects are modeled by means of polarizable continuum model. Regioselectivity of attack is studied by analyzing two contributions. The first one is the energetic ordering of the tautomers. The second is the relative inherent reactivity of nucleophilic sites in the bases. Atomic softnesses calculated by means of charge sensitivity analysis are employed for this purpose. The most reactive sites in various tautomers are identified on the ground of Li-Evans model. For adenine, it is demonstrated that both in basic and in neutral pH N7 atom possesses the most nucleophilic character. In polar solvents, N7 substitution is also most favored energetically. In basic pH and nonpolar solvents as well as in the gas phase, N9 substitution is slightly more probable. For guanine, a mixture of N7-and N9-substituted products can be expected in basic pH. In neutral pH, inherent reactivity and energy trends are opposite to each other; therefore, the substitution does not occur. Experimentally observed products of reactions with various electrophiles and in various conditions confirm the results obtained in this study.

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Section: The Energy Diagram Of Adenine Reactions With Hsupporting

confidence: 92%

Nucleophilic properties of purine bases: inherent reactivity versus reaction conditions

Stachowicz‐Kuśnierz

Korchowiec

2015

Struct Chem

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“…Quantitative parameters of the hetero-association in solution of various combinations of derivatives of nucleic acid bases have been reported for purine-purine, purine-pyrimidine and pyrimidine-pyrimidine interactions [27,70,71,[83][84][85][86][87][88][89]. Derivatives of nucleic acid bases tend to form stacking-type complexes in aqueous solutions with minor contribution, if any, from in-plane hydrogen-bonding (base-pairing), as deduced from the monotonic shift of aromatic protons to lower frequency in NMR [70,83,85,86,88,89] or the hypochromic effect in UV-vis spectroscopy [90][91][92] on increasing concentration or decreasing 16 M.P. Evstigneev temperature, and also supported by high-level quantum-chemical computations [93][94][95][96].…”

Section: Hetero-association Of Derivatives Of Nucleic Acid Basesmentioning

confidence: 99%

Hetero-association of aromatic molecules in aqueous solution

Evstigneev

2014

International Reviews in Physical Chemistry

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Knowledge of the physical chemistry of small molecules complexation (the hetero-association) in aqueous solution is increasingly important in view of the rapidly emerging branch of supramolecular chemistry dealing with the formation of heterogeneous polymeric structures having specific functional roles. In this paper, the 50-year history of scientific studies of hetero-association of heterocyclic aromatic molecules in aqueous solution has been reviewed. Some important correlations of structural and thermodynamic parameters of complexation have been reported based on large data-set of hetero-association parameters accumulated to date. The fundamental problem of 'energetic composition' of π-stacking is extensively discussed. The review has shown that there are some gaps in our understanding of heteroassociation, which provides a challenge for further studies in this area.

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“…In the case of M solution was used and absorption measured in 50-mm cells. Percentages of hypochromism ( % H ) were determined by quantitative comparison of absorption spectra of bichromophoric compounds with the summation of the spectra of reference compounds as described earlier (6). Oscillator strengths f = 4.32 x 10-" J1~(5)d5 were computed from absorption spectra using Simpson's rule.…”

Section: Electronic Absorptionmentioning

confidence: 99%

Coumarin–nucleotide base pairs. Ultraviolet absorption, fluorescence, and photochemical study

Wenska¹,

Paszỳc²

1984

Can. J. Chem.

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This paper is (ledicated to Profe.ssor Paul de Mayo or1 tile occasion of his 60th birrhdcryG R A~Y N A WENSKA and STEFAN PASZYC. Can. J. Chem. 62, 2006Chem. 62, (1984. Bichromophoric compounds containing a nucleotide base and coumarin linked with a polymethylene chain have been synthesized. A hypochromic effect was observed for adenine-coumarin pairs in contrast to the thymine containing compound. The fluorescence intensity of coumarin when bound into these systems was found to be significantly reduced. It has also been demonstrated that excitation energy is transferred from adenine or thymine to the coumarin moiety. Intermolecular dimerization of coumarin residues was observed upon irradiation of an adenine-coumarin pair. On a synthCtisC des composCs ii deux chromophores contenant un nuclkotide et une coumarine relies par une chaine polymethylene. Par opposition a ce qui est observe avec le composC semblable contenant de la thymine, on a observe un effet hypsochrome avec les paires adenine-coumarine. On a observe que I'intensitC de la fluorescence de la coumarine liCe a ces systemes est considCrablement rCduite. On a aussi demontrt qbe l'energie d'excitation est transfer6 de I'adCnine ou de la thymine vers la portion coumarine. Lors de I'irradiation d'une paire adenine-coumarine, on a observe une dimkrisation intermolCculaire des rksidus de la coumarine.[Traduit par le journal]

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Synthetic spectroscopic models related to coenzymes and base pairs. II. Evidence for intramolecular base-base interactions in dinucleotide analogs

Cited by 260 publications

References 7 publications

Nucleophilic properties of purine bases: inherent reactivity versus reaction conditions

Nucleophilic properties of purine bases: inherent reactivity versus reaction conditions

Hetero-association of aromatic molecules in aqueous solution

Coumarin–nucleotide base pairs. Ultraviolet absorption, fluorescence, and photochemical study

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