Reactivity descriptors for the hydrogen bonding ability of aliphatic alcohols

Dimitrova, Maria; Ilieva, Sylvia; Galabov, Boris

doi:10.1016/s0022-2860(03)00417-4

Cited by 5 publications

(2 citation statements)

References 30 publications

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“…On the basis of the main electrostatic character of the H-bond interaction, several electrostatic descriptors were tested to determine which one is the most properly correlated to the experimental H-bond acidity. The electrostatic potential values were calculated (i) at the nuclei, V H , because Galabov previously found very good linear correlations of this descriptor with either experimental or theoretical H-bond acidity parameters, − (ii) at a distance of 0.55 Å, V α ( r ), from the hydroxyl hydrogen atom along the OH bond, as suggested by Kenny, and (iii) at the electronic isodensity surface of 0.001 e bohr –3 , V S,max , as recommended by Bader . Atomic partial charges fitted to the electrostatic potential according to the schemes of Merz–Singh–Kollman (MK) , and Breneman and Wiberg (CHelpG) were also estimated.…”

Section: Methodsmentioning

confidence: 99%

Hydrogen-Bond Acidity of OH Groups in Various Molecular Environments (Phenols, Alcohols, Steroid Derivatives, and Amino Acids Structures): Experimental Measurements and Density Functional Theory Calculations

et al. 2013

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The hydrogen-bond (H-bond) donating strengths of a series of 36 hydroxylic H-bond donors (HBDs) with N-methylpyrrolidinone have been measured in CCl4 solution by FTIR spectrometry. These data allow the definition of a H-bond acidity scale named pKAHY covering almost three pK units, corresponding to 16 kJ mol(-1). These results are supplemented by equilibrium constants determined in CH2Cl2 for one-third of the data set to study compounds showing a poor solubility in CCl4. A systematic comparison of these experimental results with theoretical data computed in the gas phase using DFT (density functional theory) calculations has also been carried out. Quantum electrostatic parameters appear to accurately describe the H-bond acidity of the hydroxyl group, whereas partial atomic charges according to the Merz-Singh-Kollman and CHelpG schemes are not suitable for this purpose. A substantial decrease of the H-bond acidity of the OH group is pointed out when the hydroxyl moiety is involved in intramolecular H-bond interactions. In such situations, the interactions are further characterized through AIM and NBO analyses, which respectively allow localizing the corresponding bond critical point and the quantification of a significant charge transfer from the available lone pair to the σ*OH antibonding orbital. Eventually, the H-bond ability of the hydroxyl groups of steroid derivatives and of lateral chains of amino acids are evaluated on the basis of experimental and/or theoretical data.

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Section: Methodsmentioning

confidence: 99%

Hydrogen-Bond Acidity of OH Groups in Various Molecular Environments (Phenols, Alcohols, Steroid Derivatives, and Amino Acids Structures): Experimental Measurements and Density Functional Theory Calculations

et al. 2013

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“…The most negative-valued points in the MESP topography, usually indicated with the notation V min is widely used to gauge the electron donating properties of a molecule [23]. Similarly, V max is used as a parameter to measure the electron drawing abilities of a molecule [24,25].…”

Section: Molecular Electrostatic Surface Potential (Mesp)mentioning

confidence: 99%

Studying the Chemical Reactivity Properties of Cytosine and its Antiviral Analogues: Zebularine, 5-Aza-Cytosine And 5-Aza-5,6-Dihydro-Cytosine through Density Functional Theory

wang¹,

Wu²

2021

Preprint

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Zebularine, 5-aza-cytosine and 5-aza-5,6-dihydro-cytosine are structurally similar to cytosine, but their biological functions are rather different. Cytosine can be methylated which is a gene lesion that can cause human disease. On the contrary, zebularine and 5-aza-cytosine are inhibitors of DNA methylation. 5-aza-5,6-dihydro-cytosine is specifically designed to induce lethal mutagenesis in HIV for its structurally variability. Here, theoretical research into their chemical properties through density functional theory is reported. Molecular hardness and molecular electronic surface potential were analysed. Compared to cytosine, the main reason for the inability of methyl addition of zebularine is the reduced nucleophilicity of C5 atom. The lack of a hydrogen atom at N5 atom in 5-aza-cytosine is responsible for the incomplete reaction of methyl transfer. Variability of 5-aza-5,6-dihydro-cytosine is responsible for the mutagenesis treatment by paring with guanine or adenine with its different tautomers. Aspect of these chemical reactivities can be accounted for the distinctive biological functions of these molecules.

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Synthesis and fluorescence behavior of photoactive polyhydroquinoline derivatives: A combined experimental and DFT study

Phukan

Saha

Pal

et al. 2013

Journal of Molecular Structure

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Reactivity descriptors for the hydrogen bonding ability of aliphatic alcohols

Cited by 5 publications

References 30 publications

Hydrogen-Bond Acidity of OH Groups in Various Molecular Environments (Phenols, Alcohols, Steroid Derivatives, and Amino Acids Structures): Experimental Measurements and Density Functional Theory Calculations

Hydrogen-Bond Acidity of OH Groups in Various Molecular Environments (Phenols, Alcohols, Steroid Derivatives, and Amino Acids Structures): Experimental Measurements and Density Functional Theory Calculations

Studying the Chemical Reactivity Properties of Cytosine and its Antiviral Analogues: Zebularine, 5-Aza-Cytosine And 5-Aza-5,6-Dihydro-Cytosine through Density Functional Theory

Synthesis and fluorescence behavior of photoactive polyhydroquinoline derivatives: A combined experimental and DFT study

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