Effect of aqueous solvation on the structures of pyruvic acid isomers and their reactions in solution: a computational study

Kakkar, Rita; Pathak, Mallika; Gahlot, Pragya

doi:10.1002/poc.1270

Cited by 19 publications

(41 citation statements)

References 26 publications

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“…Pyruvic acid and its derivatives are compounds which exhibit keto–enol tautomerism. Pyruvic acid is an oxocarboxylic acid that is very important in the biochemistry and chemistry studies . It plays a key role in the metabolism of carbohydrates and Krebs cycle.…”

Section: Introductionmentioning

confidence: 99%

“…Also, keto–enol tautomerism and isomerization in pyruvic acid have been well studied experimentally and theoretically . Kakkar et al theoretically investigated the stability of isomers of pyruvic acid in the gas phase using the density functional theory.…”

Section: Introductionmentioning

confidence: 99%

“…They found that a keto form with trans methylgroup‐C keto ‐C acid ‐O hydroxyl and cis C keto ‐C acid ‐O‐H, and one methyl hydrogen in a synperiplanar position with respect to the keto‐oxygen, is the most stable isomer. In another study, Kakkar et al studied the mechanism of decarboxylation of pyruvic acid and its various isomers and calculated its pK a in aqueous solution at the B3LYP level of theory. The keto–enol tautomerism in pyruvic acid has been studied by Fourier transform‐ infra red spectroscopy (FT‐IR) in three solvents including CCl 4 , CH 2 Cl 2 , and benzene at room temperature .…”

Section: Introductionmentioning

confidence: 99%

“…Keto–enol tautomerism of pyruvic acid is mainly studied experimentally . The theoretical studies are almost related to the stability of pyruvic acid tautomers and isomers in the gas phase and solution . The keto–enol tautomerism processes between the enol and keto forms of pyruvic acid have not been studied, theoretically.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical study on keto–enol tautomerism and isomerization in pyruvic acid

Valadbeigi

Farrokhpour

2013

Int J of Quantum Chemistry

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Isomerization and tautomerism of 12 isomers of pyruvic acid including 4 keto and 8 enol forms were studied at the MP2 and B3LYP levels of theory using 6‐311++G(2df,p) basis set, separately. Activation energy (Ea), imaginary frequency (υ), and Gibbs free energy (ΔG#) of the considered isomerization and tautomerism reactions were calculated. Interconversion of the enol forms proceeds through two paths: (i) proton transfer and (ii) internal rotation. Activation energies for the proton transfer paths were in the range of 125–145 kJ/mol and for the internal rotation paths were in the range of 5–45 kJ/mol. Keto–enol tautomerism of pyruvic acid proceeds only through proton transfer route and their activation energies were in the range of 200–300 kJ/mol. Effect of microhydration on the transition state structures and activation energies was also investigated. It was found that the presence of a water molecule catalyzes the isomerization and tautomerism reactions of pyruvic acid so that the activation energies decrease. © 2013 Wiley Periodicals, Inc.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Theoretical study on keto–enol tautomerism and isomerization in pyruvic acid

Valadbeigi

Farrokhpour

2013

Int J of Quantum Chemistry

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“…Pyruvic acid, because of the presence of the keto group, can undergo keto-enol tautomerism [26], a chemical equilibrium between the keto and enol forms:…”

Section: Adsorption Of Carboxylic Acids On Ga 2 O 3 Nwsmentioning

confidence: 99%

Interaction of functionalized Ga2O3 NW-based room temperature gas sensors with different hydrocarbons

Mazeina

Bermudez

Perkins

et al. 2010

Sensors and Actuators B: Chemical

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DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution

Buemi

2009

J of Physical Organic Chem

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DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution Giuseppe Buemi a * The molecular geometries of the possible conformations of formic, oxalic, glyoxylic and pyruvic acids have been fully optimized at DFT B3LYP/6-311RRG(d,p) levels of calculation in vacuum as well as in water and acetone solution. Solutions were treated according to the SCRF PCM approach but some formic acid-water and formic acid-acetone clusters as well as adducts of oxalic acid with two or four water molecules were also taken into account for testing the importance of specific solute-solvent effects. All the most stable isomers of the title compounds are characterized by weak intramolecular hydrogen bonds, whose strengths (E HB ) cannot be correctly estimated as stability difference between the open and chelate forms since the energy of the former isomer is, in turn, stabilized by a weak hydrogen bridge due to the formic acid moiety. Following the Rotation Barrier Method (RBM), proposed some years ago, E HB in the examined molecules (gas phase) falls in the range of 18-22 kJ/mol for oxalic acid (9.6 kJ/mol for the c-C-t isomer), 16.8 kJ/mol for glyoxylic acid and 19.8 kJ/mol for pyruvic acid. Most of them disappear at all, or nearly at all, both in acetone and aqueous solution, in consequence of the solvent effect. The frequencies of the OH and C --O stretching modes, calculated according to the anharmonic oscillator model, are in very good agreement with the experimental literature data, where available.Specific solvent effects can be obtained by considering the adduct with at least one solvent molecule. Figure 2 shows the lowest energy hydrogen bonded complexes formed by trans-and

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Effect of aqueous solvation on the structures of pyruvic acid isomers and their reactions in solution: a computational study

Cited by 19 publications

References 26 publications

Theoretical study on keto–enol tautomerism and isomerization in pyruvic acid

Theoretical study on keto–enol tautomerism and isomerization in pyruvic acid

Interaction of functionalized Ga2O3 NW-based room temperature gas sensors with different hydrocarbons

DFT study of the hydrogen bond strength and IR spectra of formic, oxalic, glyoxylic and pyruvic acids in vacuum, acetone and water solution

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