The applicability of the dimeric heterosynthon concept to molecules with equivalent binding sites. A DFT study of crystalline urea–H<sub>2</sub>O<sub>2</sub>

Medvedev, Alexander G.; Shishkina, Anastasia V.; Prikhodchenko, Petr V.; Lev, Ovadia; Vener, Mikhail V.

doi:10.1039/c5ra02498f

Cited by 17 publications

(22 citation statements)

References 104 publications

(124 reference statements)

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“…The particular value of E HB (−Δ H HB ) vary by up to ~10 kJ mol −1 depending on the scheme. Similar results were obtained earlier …”

Section: Resultssupporting

confidence: 93%

“…Formation of the two DH‐bonds agrees with the literature data . In gas phase models H 2 O 2 always forms one DH‐bond . This indicates the need to use periodic models to adequately describe the heterogenic catalytic reactions of H 2 O 2 .…”

Section: Resultssupporting

confidence: 83%

“…The quantum theory of atoms in molecules and crystals (Bader) analysis of the periodic electron density was performed with TOPOND . The calculation methodology is presented elsewhere . The energy of the considered hydrogen bond, energy E HB , was calculated according to ref.…”

Section: Methodsmentioning

confidence: 99%

“…It is known that cluster approaches give an adequate description of covalent bonding . However, not all possible noncovalent interactions are realized with these approaches . Current DFT calculations are often performed using small metal clusters less than 1 nm .…”

Section: Introductionmentioning

confidence: 99%

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Effect of aluminum vacancies on the H₂O₂ or H₂O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

Medvedev

Mikhaylov

Chernyshov

et al. 2019

Int J of Quantum Chemistry

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The adsorption of a single H 2 O 2 or H 2 O molecule on a family of periodic slab models of γ-AlOOH is studied by solid-state DFT. The single H 2 O 2 or Н 2 О molecule interacts with the perfect (010) slab by intermolecular hydrogen bonds (H-bonds). In the models of γ-AlOOH with oxygen and aluminum vacancies, H 2 O 2 or Н 2 О also forms covalent OÁÁÁAl bonds. The energies of covalent OÁÁÁAl and H-bonds are estimated by a combined approach based on simultaneous consideration of the total binding energies with BSSE correction and empirical schemes of the Н-bond energy evaluation. The OÁÁÁAl bond energy ranges from~75 to~156 kJ mol −1 . The total energy of H-bond interactions in the case of H 2 O 2 exceeds that of Н 2 О by~30 kJ mol −1 for all considered slab models. In contrast to Н 2 О, a H 2 O 2 molecule always forms two H-bonds as the proton donor. The energy of these bonds noticeably increase on defect γ-AlOOH surfaces in comparison with the perfect slab due to formation of short (strong) H-bonds by adsorbed H 2 O 2 . K E Y W O R D S catalytic center, intermolecular H-bond energy/enthalpy, oxygen and aluminum vacancies, perfect and defect slab models, the Bader analysis of periodic electron density

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“…The particular value of E HB (−Δ H HB ) vary by up to ~10 kJ mol −1 depending on the scheme. Similar results were obtained earlier …”

Section: Resultssupporting

confidence: 93%

Section: Resultssupporting

confidence: 83%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Effect of aluminum vacancies on the H₂O₂ or H₂O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

Medvedev

Mikhaylov

Chernyshov

et al. 2019

Int J of Quantum Chemistry

View full text Add to dashboard Cite

show abstract

“…(1). The latter approach provides reasonable values for singlecomponent [37,40] and two-component [24,46] It is assumed that the E latt energy corresponds to the sublimation enthalpy ∆H 0 subl , extrapolated to 0 K. According to [47], the value of the sublimation enthalpy at given temperature T can be written as:…”

Section: Calculation Proceduresmentioning

confidence: 99%

Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

et al. 2015

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Cocrystal screening of 4-hydroxybenzamide with a number of salicylates (salicylic acid, SA; 4-aminosalicylic acid, PASA; acetylsalicylic acid, ASA; and salicylsalicylic acid, SSA) was conducted to confirm the formation of two cocrystals, [SA+4-OHBZA] (1:1) and [PASA+4-OHBZA] (1:1). Their structures were determined using single-crystal X-ray diffraction, and the hydrogen-bond network topology was studied. Thermodynamic characteristics of salicylic acid cocrystal sublimation were obtained experimentally. It was proved that PASA cocrystallization with 4-OHBZA makes the drug more stable and prevents the irreversible process of decarboxylation of PASA resulting in formation of toxic 3-aminophenol. The pattern of non-covalent interactions in the cocrystals is described quantitatively using solid-state density functional theory followed by Bader analysis of the periodic electron density. It has been found that the total energy of secondary interactions between synthon atoms and the side hydroxyl group of the acid molecule in [SA+4-OHBZA] (1:1) and [PASA+4-OHBZA] (1:1) cocrystals is comparable to the energy of the primary acid-amide heterosynthon. The theoretical value of the sublimation enthalpy of [SA+4-OHBZA], 231 kJ/mol, agrees fairly well with the experimental one, 272 kJ/mol. The dissolution experiments with [SA+4-OHBZA] have proved that the relatively large cocrystal stability in relation to the stability of its components has a negative effect on the dissolution rate and equilibrium solubility. The [PASA+4-OHBZA] (1:1) cocrystal showed an enhancement of apparent solubility compared to that of the corresponding pure active pharmaceutical ingredient, while their intrinsic dissolution rates are comparable.

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An H₂O₂ Molecule Stabilized inside Open‐Cage C₆₀ Derivatives by a Hydroxy Stopper

Murata

Huang

Hasegawa

et al. 2021

Chemistry A European J

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An H2O2 molecule was isolated inside hydroxylated open‐cage fullerene derivatives by mixing an H2O2 solution with a precursor molecule followed by reduction of one of carbonyl groups on its orifice. Depending on the reduction site, two structural isomers for H2O2@open‐fullerenes were obtained. A high encapsulation ratio of 81 % was attained at low temperature. The structures of the peroxosolvate complexes thus obtained were studied by 1H NMR spectroscopy, X‐ray analysis, and DFT calculations, showing strong hydrogen bonding between the encapsulated H2O2 and the hydroxy group located at the center of the orifice. This OH group was found to act as a kinetic stopper, and the formation of the hydrogen bonding caused thermodynamic stabilization of the H2O2 molecule, both of which prevent its escape from the cage. One of the peroxosolvates was isolated by HPLC, affording H2O2@open‐fullerene with 100 % encapsulation ratio, likely due to the intramolecular hydrogen‐bonding interaction.

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The applicability of the dimeric heterosynthon concept to molecules with equivalent binding sites. A DFT study of crystalline urea–H₂O₂

Abstract: The limited applicability of the dimeric heterosynthon concept to a two-component urea–H2O2crystal is reported.

Cited by 17 publications

References 104 publications

Effect of aluminum vacancies on the H₂O₂ or H₂O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

Effect of aluminum vacancies on the H₂O₂ or H₂O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

An H₂O₂ Molecule Stabilized inside Open‐Cage C₆₀ Derivatives by a Hydroxy Stopper

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The applicability of the dimeric heterosynthon concept to molecules with equivalent binding sites. A DFT study of crystalline urea–H2O2

Abstract: The limited applicability of the dimeric heterosynthon concept to a two-component urea–H2O2crystal is reported.

Cited by 17 publications

References 104 publications

Effect of aluminum vacancies on the H2O2 or H2O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

Effect of aluminum vacancies on the H2O2 or H2O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study

An H2O2 Molecule Stabilized inside Open‐Cage C60 Derivatives by a Hydroxy Stopper

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The applicability of the dimeric heterosynthon concept to molecules with equivalent binding sites. A DFT study of crystalline urea–H₂O₂

Effect of aluminum vacancies on the H₂O₂ or H₂O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

Effect of aluminum vacancies on the H₂O₂ or H₂O interaction with a gamma‐AlOOH surface. A solid‐state DFT study

An H₂O₂ Molecule Stabilized inside Open‐Cage C₆₀ Derivatives by a Hydroxy Stopper