<b><i>Ab initio</i></b> molecular dynamics study of ascorbic acid in aqueous solution

Costanzo, Francesca; Sulpizi, Marialore; VandeVondele, Joost; Valle, Raffaele Guido Della; Sprik, Michiel

doi:10.1080/00268970601126718

Cited by 14 publications

(12 citation statements)

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To sum up, our observed bands for AH 2 and AH − compare quite well with other spectral modeling results (4,15,23,26,46,(52)(53)(54)(55)(56)(57)(58)(59) and with the available experimental bands in the literature (39)(40)(41)(42)(43)(44)(45). We note, however, that the AH 2 sample of Panicker et al (45), presumably solid, seems to have been not entirely pure, because the Raman spectrum Table 7 Measured Raman spectral bands (in cm ) and assignments for aqueous solutions of ascorbic acid and sodium ascorbates, compared to literature values (39,44,46,48).…”

Section: Sodium Ascorbatesupporting

confidence: 74%

“…To exclude O 2 as much as possible the method described in the Experimental section was absolutely necessary. We assume that A 2− ions react with electrons to form radicals (19,23), and the radicals emit fluorescence, which makes it impossible to obtain Raman spectra with visible laser lines shortly after the NaOH addition. It was, however, possible for some minutes to obtain Raman data for the A 2− ion before the solution was ruined by fluorescing radicals.…”

Section: A 2−mentioning

confidence: 99%

“…At even higher basic pH values isomerization at C4 may take place (20). The acid/base and oxidation/reduction reactions of ascorbic acid are coupled, and in highly basic solutions and under the presence of oxygen the molecules are easily oxidized to various radicals, forming in the end salts of the dehydroascorbic acid, C 6 H 6 O 6 (ascorbic acid that has lost H2 and H3 protons and two electrons) (19,(21)(22)(23). Quite stable free radicals of ascorbic acid seem to be formed via ionization of the O3 or O2 anions, and also a stable di-radical seems to exist via ionization of the O3 O2 di-anion (4).…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Investigation ofL(+)-Ascorbic acid with Raman spectroscopy in visible and UV light

Berg

2014

Applied Spectroscopy Reviews

View full text Add to dashboard Cite

show abstract

Section: Sodium Ascorbatesupporting

confidence: 74%

Section: A 2−mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Investigation ofL(+)-Ascorbic acid with Raman spectroscopy in visible and UV light

Berg

2014

Applied Spectroscopy Reviews

View full text Add to dashboard Cite

show abstract

“…This issue has been addressed by Costanzo et al using DFT calculations and molecular dynamics simulations. They show that all three exocyclic oxygen atoms carry significant negative charge in both AscH − and Asc •− , with all the atomic charges being smaller in the radical 40. Molecular dynamics simulations indicate that in aqueous solution, the enolate oxygen of AscH − is the preferred hydrogen bonding site.…”

Section: Discussionmentioning

confidence: 99%

Tuning of the Thermochemical and Kinetic Properties of Ascorbate by Its Local Environment: Solution Chemistry and Biochemical Implications

2010

View full text Add to dashboard Cite

Ascorbate (Vitamin C) is a ubiquitous biological cofactor. While its aqueous solution chemistry has long been studied, many in vivo reactions of ascorbate occur in enzyme active sites or at membrane interfaces, which have varying local environments. This report shows that the rate and driving force of oxidations of two ascorbate derivatives by the TEMPO radical (2,2′-6,6′-tetramethylpiperidine-1-oxyl) in acetonitrile are very sensitive to the presence of various additives. These reactions proceed by the transfer of a proton and an electron (a hydrogen atom), as is typical of biological ascorbate reactions. The measured rate and equilibrium constants vary substantially with added water or other polar solutes in acetonitrile solutions, indicating large shifts in the reducing power of ascorbate. The correlation of rate and equilibrium constants indicates that this effect has a thermochemical origin rather than being a purely kinetic effect. This contrasts with previous examples of solvent effects on hydrogen atom transfer reactions. Potential biological implications of this apparently unique effect are discussed.

show abstract

“…The carbonyl O atom adjacent to the side chain (in Fig. 1) has been proven to be the most acidic site [14][15][16][17]. Obviously, the study of the coupling interactions between the monoanionic Vc and MG should be the first step toward understanding the augment role of Vc for the anticancer effect of MG.…”

Section: Introductionsmentioning

confidence: 99%

Explorations of the nature of the coupling interactions between vitamin C and methylglyoxal: a DFT study

Zhai

et al. 2011

Struct Chem

View full text Add to dashboard Cite

As the first step toward understanding the augment role of vitamin C (Vc) for the anticancer effect of methylglyoxal (MG), the nature of the coupling interactions between Vc and MG has been systematically investigated at the B3LYP/6-311??G** level of theory in combination with the atoms in molecules (AIM) theory, natural bond orbital (NBO) method, and energy decomposition analysis (EDA). The possible stable complexes have been located on their potential energy surface (PES). Most of them are characterized by one or two intermolecular H-bonds with the binding energies varying from -11.1 to -2.0 kcal/mol. AIM analyses suggest that all the intermolecular H-bonds have been predominated by the electrostatic interaction. A good linear correlation between the intermolecular H-bond distance and the electron density as well as its Laplacian at the bond critical point of the intermolecular H-bond has been observed. Depending on the selected coupling modes between Vc and MG, the origin of the blue-shifts of the stretching vibrational frequencies of different C-H bonds has been elucidated. Additionally, the inherent reason for the positive role of Vc in the anticancer process for MG has been verified through the investigation of the one-electron oxidation behaviors of the most stable complex.

show abstract

Ab initio molecular dynamics study of ascorbic acid in aqueous solution

Cited by 14 publications

References 41 publications

Investigation ofL(+)-Ascorbic acid with Raman spectroscopy in visible and UV light

Investigation ofL(+)-Ascorbic acid with Raman spectroscopy in visible and UV light

Tuning of the Thermochemical and Kinetic Properties of Ascorbate by Its Local Environment: Solution Chemistry and Biochemical Implications

Explorations of the nature of the coupling interactions between vitamin C and methylglyoxal: a DFT study

Contact Info

Product

Resources

About