Hydration effect on the stability of the keto-enol tautomers of 5-hydroxy-6-methyluracil

Dautova, I. F.; Ivanov, S. P.; Хурсан, С. Л.

doi:10.1007/s10947-009-0162-4

Cited by 8 publications

(6 citation statements)

References 33 publications

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“…Previous the quantum chemical calculations had shown that the diketo form of HMU ( I ) is energetically the most favorable both in the gas phase and in case of hydration . It is stabilized by the intramolecular hydrogen bond.…”

Section: Resultsmentioning

confidence: 99%

“…Previous the quantum chemical calculations had shown that the diketo form of HMU (I) is energetically the most favorable both in the gas phase 29 and in case of hydration. 30,31 It is stabilized by the intramolecular hydrogen bond. Therefore, this structure is considered as the building block of the HMU dimers (in Scheme 1, the energies are in kJ/mol).…”

Section: Resultsmentioning

confidence: 99%

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Specific Intermolecular Interactions in the Supramolecular Structure of 5‐Hydroxy‐6‐Methyluracil: A DFT Study of the Hydrogen‐bonded Dimers

Shayakhmetova

Khamitov

Мустафин

et al. 2016

J Chinese Chemical Soc

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Studying the self‐assembly of uracil derivatives has great importance for biochemistry and nanotechnology. For example, modification of the sorbent surfaces by 5‐hydroxy‐6‐methyluracil (HMU) enhances their adsorption activity. It is assumed that these changes are caused by the self‐assembly of the network‐like supramolecular associates of the uracil derivative on the sorbent surface. In the present work, the relative stabilities of 15 hydrogen‐bonded dimers HMU have been studied by the TPSSh/TZVP density functional theory method and the strengths of the noncovalent interactions analyzed in terms of the reduced density gradient and natural bond orbital approaches. It was found that the symmetric dimer stabilized by two intermolecular hydrogen bonds N1–H∙∙∙O–C2 (dimer 1‐1) is the most stable. This suggests that the self‐assembly of HMU should occur through the intermediate formation of the dimer 1‐1. The results may be useful for understanding the processes of self‐assembly of the uracil derivatives and the rationalized design of the uracil‐based supramolecular structures with specific properties.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Specific Intermolecular Interactions in the Supramolecular Structure of 5‐Hydroxy‐6‐Methyluracil: A DFT Study of the Hydrogen‐bonded Dimers

Shayakhmetova

Khamitov

Мустафин

et al. 2016

J Chinese Chemical Soc

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“…In fact, the content of minor tautomers of uracil, thymine, and 5-fluorouracil (FU) was found to be ∼10 –13 %, as obtained by calculations using the 3-21G basis set . On the other hand, when a more advanced base set, 6-31+G(d,p), was used, the amount of rare tautomeric FU forms was estimated to be around 10 –4 –10 –8 %. , Besides enhancing the level of a quantum-chemical approximation, it should be noted that improving the calculation model, in particular, by describing the solvation effects as adequately as possible, also significantly affects the calculated energies of tautomeric forms of uracils. , …”

Section: Introductionmentioning

confidence: 95%

“…20,21 Besides enhancing the level of a quantum-chemical approximation, it should be noted that improving the calculation model, in particular, by describing the solvation effects as adequately as possible, also significantly affects the calculated energies of tautomeric forms of uracils. 22,23 A real breakthrough in the experimental detection of keto− enol tautomers of uracils was achieved by luminescent methods. In ref 24, based on changes in the fluorescence (FL) spectra of thymine aqueous solutions upon variation of the excitation light wavelength, it was first suggested that the long-wave component of the FL spectrum whose contribution increases as the photoexcitation energy decreases is due to the emission of keto−enol forms of the pyrimidine base.…”

Section: ■ Introductionmentioning

confidence: 99%

Luminescent and DFT Study of Keto–Enol Tautomers of 5-Fluorouracil and Its Derivatives in Aqueous Solutions

et al. 2019

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Fluorescence (FL) spectra were recorded and identified for the following 5-fluorouracil (FU) tautomers: 5fluoropyrimidine-2,4(1H,3H)-dione (A), 5-fluoro-2-hydroxypyrimidine-4(3H)-one (B), and 5-fluoro-4-hydroxypyrimidine-2(1H)-one (D), as well as the corresponding tautomers A and D of 1-(tetrahydrofuranyl-2)-5-fluorouracil and 1methyl-5-fluorouracil, tautomers A and B of 3-methyl-5fluorouracil, and the diketo tautomer of 1,3-dimethyl-5fluorouracil. It was shown that the FL of rare tautomers of FU derivatives occurs by the excitation of uracil homoassociates followed by intramolecular proton transfer (IPT), formation of a pair of rare tautomers, and radiative deactivation of one of them. The FL quantum yields φ i were estimated. In the case of rare tautomers, the φ i value includes the probability of IPT in the homoassociate, and density functional theory calculations in the TPSSTPSS/6-311+G(d,p) approximation were used to determine the relative energies of tautomers, associated FU forms, and their spectral properties that agree with the observed luminescence pattern.

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“…The stability of rotational isomers strictly depends on the possibility of interactions between the lone pairs on the hydroxyl and imino nitrogen atoms. 27,[30][31][32] In this paper, only the most favorable rotational isomeric forms are considered. We found that applying an electric field to the reacting molecules is a promising catalytic approach.…”

Section: Introductionmentioning

confidence: 99%

Proton transfer theoretical study catalyzed by 5‐chlorouracil

Cheng

2024

J of Physical Organic Chem

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In this study, the density functional M06‐2X/6‐311++G(3df,3pd) method was employed to investigate the mutual isomerization reaction mechanism of 5‐chlorouracil from diketone to diol under the catalysis of water, methanol, formic acid, and an electric field. Parameters such as reaction enthalpy, activation energy, activation Gibbs free energy, and proton transfer reaction rate were obtained. The computational results show that under the same conditions, formic acid demonstrates the best catalytic effect, while the influence of electric field catalysis on the reaction barrier is minimal.

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Hydration effect on the stability of the keto-enol tautomers of 5-hydroxy-6-methyluracil

Cited by 8 publications

References 33 publications

Specific Intermolecular Interactions in the Supramolecular Structure of 5‐Hydroxy‐6‐Methyluracil: A DFT Study of the Hydrogen‐bonded Dimers

Specific Intermolecular Interactions in the Supramolecular Structure of 5‐Hydroxy‐6‐Methyluracil: A DFT Study of the Hydrogen‐bonded Dimers

Luminescent and DFT Study of Keto–Enol Tautomers of 5-Fluorouracil and Its Derivatives in Aqueous Solutions

Proton transfer theoretical study catalyzed by 5‐chlorouracil

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