Substituent effects on some calculated NMR data in T-shaped configuration of benzene dimer

Masoodi, Hamid Reza; Zakarianezhad, Mohammad; Bagheri, Sotoodeh; Makiabadi, Batoul; Shool, Motahareh

doi:10.1016/j.cplett.2014.09.021

Cited by 7 publications

(6 citation statements)

References 45 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Configurations with minor variations in angles less than 30° are suggested to be similar in energy by previous theoretical studies . It is also suggested that various substituent effects on the relative stability of stacking. , Third, the favorable London dispersion interactions and, therefore, π–π stacking may be underestimated with the fixed partial charges in the classical MD force field. , London dispersion interactions are originated from instantaneous multipole/induced multipole charge fluctuations, which make it essential to describe the polarizability accurately. The previous studies with molecular mechanics force fields slightly underestimated π–π interactions. − It was also suggested that π–π interactions in water have higher energy minimum than that of the solvent-free state due to the damping by solvent competition and the entropic effects. ,, This may explain why the stacking arrangements are not well-defined in the filament system.…”

Section: Resultsmentioning

confidence: 73%

“…21 It is also suggested that various substituent effects on the relative stability of stacking. 41,42 Third, the favorable London dispersion interactions and, therefore, π ‒ π stacking may be underestimated with the fixed partial charges in the classical MD force field. 43,44 London dispersion interactions are originated from instantaneous multipole/induced multipole charge fluctuations, which make it essential to describe the polarizability accurately.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

π–π Stacking Mediated Chirality in Functional Supramolecular Filaments

et al. 2016

View full text Add to dashboard Cite

While a great diversity of peptide-based supra-molecular filaments have been reported, the impact of an auxiliary segment on the chiral assembly of peptides remains poorly understood. Herein we report on the formation of chiral filaments by the self-assembly of a peptide-drug conjugate containing an aromatic drug camptothecin (CPT) in a computational study. We find that the chirality of the filament is mediated by the π‒π stacking between CPTs, not only by the well-expected intermolecular hydrogen bonding between peptide segments. Our simulations show that π‒π stacking of CPTs governs the early stages of the self-assembly process, while a hydrogen bonding network starts at a relatively later stage to contribute to the eventual morphology of the filament. Our results also show the possible presence of water within the core of the CPT filament. These results provide very useful guiding principles for the rational design of supramolecular assemblies of peptide conjugates with aromatic segments.

show abstract

Section: Resultsmentioning

confidence: 73%

Section: Resultsmentioning

confidence: 99%

π–π Stacking Mediated Chirality in Functional Supramolecular Filaments

et al. 2016

View full text Add to dashboard Cite

show abstract

“…The NMR data reflect the electronic structure molecules and therefore can be a powerful tool in characterizing interactions [70][71][72][73][74][75][76][77][78][79]. Table 1 Binding energies (in kcal mol -1 ), the distance between center of rings, intermolecular halogen bond length and Cl-F bond length (in Å ) and the Hammett electronic parameters in X-ben||pyrÁÁÁCl-F complexes at MP2/aug-ccpVDZ level of theory The effect of p-p stacking interactions on the twobonded spin-spin coupling constant 2X J(N-F) across 15 NÁÁÁ 35 Cl-19 F halogen bond was explored in X-ben||-pyrÁÁÁCl-F complexes.…”

Section: Spin-spin Coupling Constants Across 15 Nááá 35 Cl-19 F Halogmentioning

confidence: 99%

Theoretical investigation of the nature and strength of simultaneous interactions of π–π stacking and halogen bond including NMR, SAPT, AIM and NBO analysis

2016

View full text Add to dashboard Cite

Ab initio MP2/aug-cc-pVDZ calculations were performed to investigate mutual effect between p-p stacking and halogen bond interactions in X-ben||pyrÁÁÁCl-F complexes (X = CN, F, Cl, Br, CH 3 , OH and H where || and ÁÁÁ denote p-p stacking and halogen bonds). The results indicate the cooperativity of p-p stacking and halogen bonds in these complexes. This effect was discussed in terms of the energetic, geometrical parameters and chargetransfer properties of the complexes. To explore on the two-bonded spin-spin coupling constant 2X

show abstract

“… 18 , 21 , 28 Electron-withdrawing substituents on the C–H donor reduce the electron density around the hydrogens at the interface between the two rings, resulting in a stronger interaction. 21 , 28 , 29 The interaction is also strengthened if the substituent on the H-donating ring is in close proximity to the accepting ring. 28 …”

Section: Introductionmentioning

confidence: 99%

“…The strengths of T-shaped benzene interactions depend on the electron-withdrawing or -donating nature of the substituent and on whether the substitution is on the arene C–H donor or on the acceptor benzene. ,, Electron-withdrawing substituents on the C–H donor reduce the electron density around the hydrogens at the interface between the two rings, resulting in a stronger interaction. ,, The interaction is also strengthened if the substituent on the H-donating ring is in close proximity to the accepting ring …”

Section: Introductionmentioning

confidence: 99%

Physical Mechanisms Governing Substituent Effects on Arene–Arene Interactions in a Protein Milieu

et al. 2020

View full text Add to dashboard Cite

Arene–arene interactions play important roles in protein–ligand complex formation. Here, we investigate the characteristics of arene–arene interactions between small organic molecules and aromatic amino acids in protein interiors. The study is based on X-ray crystallographic data and quantum mechanical calculations using the enzyme acetylcholinesterase and selected inhibitory ligands as a model system. It is shown that the arene substituents of the inhibitors dictate the strength of the interaction and the geometry of the resulting complexes. Importantly, the calculated interaction energies correlate well with the measured inhibitor potency. Non-hydrogen substituents strengthened all interaction types in the protein milieu, in keeping with results for benzene dimer model systems. The interaction energies were dispersion-dominated, but substituents that induced local dipole moments increased the electrostatic contribution and thus yielded more strongly bound complexes. These findings provide fundamental insights into the physical mechanisms governing arene–arene interactions in the protein milieu and thus into molecular recognition between proteins and small molecules.

show abstract

Substituent effects on some calculated NMR data in T-shaped configuration of benzene dimer

Cited by 7 publications

References 45 publications

π–π Stacking Mediated Chirality in Functional Supramolecular Filaments

π–π Stacking Mediated Chirality in Functional Supramolecular Filaments

Theoretical investigation of the nature and strength of simultaneous interactions of π–π stacking and halogen bond including NMR, SAPT, AIM and NBO analysis

Physical Mechanisms Governing Substituent Effects on Arene–Arene Interactions in a Protein Milieu

Contact Info

Product

Resources

About