Dataset Information

Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions.

ABSTRACT: A series of seven N-phenylamides [R-C(O)NHPh, in which R: CH₃, C(CH₃)₃, Ph, CF₃, CCl₃, CBr₃, and H] were used as models in this study. Molecular packing and intermolecular interactions were evaluated by theoretical calculations, solution NMR, and quantum theory of atoms in molecules analyses. Crystallization mechanisms were proposed based on the energetic and topological parameters using the supramolecular cluster as demarcation. Concentration-dependent ¹H NMR experiments corroborated the proposed interactions between molecules. For all compounds (except for R: H, which initially formed tetramers), layers (two-dimensional) or chains (one-dimensional) were formed in the first stage of the proposed crystallization mechanisms. The presence of strong intermolecular NH···O=C interactions promoted the first stages. The study in solution provided different values of association constant (K _ass) governed by the hydrogen bond NH···O=C, showing that the stronger interactions are directly influenced by the substituent steric hindrance. A correlation between K _{ass(NH···O=C)} from the solution and the NH···O=C interaction energy in the crystal showed a good trend.

SUBMITTER: Pagliari AB

PROVIDER: S-EPMC6645157 | biostudies-literature | 2018 Oct

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions.

Pagliari Anderson B AB Orlando Tainára T Salbego Paulo R S PRS Zimmer Geórgia C GC Hörner Manfredo M Zanatta Nilo N Bonacorso Helio G HG Martins Marcos A P MAP

ACS omega 20181022 10

A series of seven N-phenylamides [R-C(O)NHPh, in which R: CH3, C(CH3)3, Ph, CF3, CCl3, CBr3, and H] were used as models in this study. Molecular packing and intermolecular interactions were evaluated by theoretical calculations, solution NMR, and quantum theory of atoms in molecules analyses. Crystallization mechanisms were proposed based on the energetic and topological parameters using the supramolecular cluster as demarc ...[more]

PMID: 31458083

Similar Datasets

Project description:Previous investigations were conducted on two concentrations of DNA solution: 4 mg/mL, for which it has been shown that no supramolecular organization is induced under flow at low shear rates; and 10 mg/mL, in which a liquid crystalline-type texture is formed under flow at low shear rates, attesting to an orientation of pre-organized chains. Rheological experiments are discussed and their results supported by small-angle X-ray scattering (SAXS) and flow birefringence visualization experiments. Scattering from polyelectrolytes has a characteristic signal, which is here observed in SAXS, showing a strong correlation peak between charged chains in water, for both concentrations. This peak is weaker in the presence of 0.01 M NaCl and suppressed in salt excess at 0.1 M NaCl. No plateau in the ?( ? ? ) plot was observed in analysis of rheological experiments on low DNA concentration (4 mg/mL). As typically observed in polyelectrolyte systems both the dynamic moduli and shear viscosity were higher in water as electrostatic forces dominate, than in the presence of salt, especially at low shear rates. The rheological results for concentrations of 0.01 M NaCl are lower than in water as expected due to partial screening of electrostatic repulsions. Rheological data for concentrations of 0.1 M NaCl are unexpected. Electrostatic forces are partially screened in the low salt concentration, leading to a drop in the rheological values. For high salt concentration there are no longer interchain repulsions and so steric interactions dominate within the entangled network leading to the subsequent increase in rheological parameters. Regardless of the solvent, at high shear rates the solutions are birefringent. In the 10 mg/mL case, under flow, textures are formed at relatively low shear rate before all the chains align going to a pseudonematic liquid crystalline phase at high shear rate. The electrostatic repulsion between semi-rigid chains induces a correlation between the chains leading to an electrostatic pseudo-gel in water and loosely in 0.01 M NaCl at low stress applied. To the best of our knowledge, this is the first time that such behavior is observed. In 0.1 M NaCl, DNA behavior resembles the corresponding neutral polymer as expected for polyelectrolyte in salt excess, exhibiting a yield stress. When texture appears in water and in 0.01 M NaCl, a critical transition is observed in rheological curves, where the viscosity decreases sharply at a given critical shear stress corresponding to a plateau in the ?( ? ? ) plot also observed in creep transient experiment.

Dataset Information

Supramolecular Packing of a Series of N-Phenylamides and the Role of NH···O=C Interactions.

Publications

Supramolecular Packing of a Series of <i>N</i>-Phenylamides and the Role of NH···O=C Interactions.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets