Mesomorphic, Computational Investigations and Dyeing Applications of Laterally Substituted Dyes.

Two groups of laterally substituted non-mesomorphic and liquid crystalline materials bearing monoazo group were prepared and investigated via experimental and theoretical techniques. The molecular structures of the designed dyes were evaluated by FT-IR and NMR spectroscopic analyses. Mesomorphic examinations for all synthesized dyes were investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Results revealed that, the thermal and optical properties of investigated compounds are mainly dependent on their molecular geometry. The optimized geometries of the azo derivatives and their electronic absorption of the dyes were carried out using the B3LYP/6-311G level of the DFT method. The azo dyes were measured for their dyeing performance on polyester fabrics. The dyed fabrics have excellent fastness properties with a color strength of 1.49-3.43 and an exhaustion rate of 82-64%. The chemical descriptor parameters of disperse azo dyes in gas phase were calculated and correlated with dyeing parameters.

Experimental and Theoretical Investigations of Three-Ring Ester/Azomethine Materials.

New three-ring ester/azomethine homologues series, (E)-4-((4-hydroxybenzylidene)amino)phenyl 4-(alkoxy)benzoate In, were prepared and their properties were investigated experimentally and theoretically. FT-IR, NMR, and elemental analyses were used to confirm the chemical structures of the synthesized compounds. The mesomorphic activities of the planned homologues were evaluated using differential scanning calorimetry (DSC) and polarized optical microscopy. All of the homologous examined were found to have non-mesomorphic properties. Theoretical calculations using the density functional theory (DFT) were used to validate the experimental data and determine the most stable conformation of the synthesized compounds. All calculated conformers' thermal properties, dipole moments, and polarizability were discussed. The results show that the terminal alkoxy chain length affects the thermal parameters of the conformers. The correlations between these parameters' values and the conformer type were demonstrated. The base component was expected to be in two conformers according to the orientation of the N atom of imine-linkage. DFT calculations revealed the more probable of the two possible conformers, and the incorporation of the alkoxy terminal chain in one position affect its geometrical and mesomerphic characteristics.

Polymorphic Phases of Supramolecular Liquid Crystal Complexes Laterally Substituted with Chlorine.

New supramolecular complexes, based on H-bonding interactions between 4-(pyridin-4-yl) azo-(2-chlorophenyl) 4-alkoxybenzoates (Bn) and 4-[(4-(n-hexyloxy)phenylimino)methyl]benzoic acid (A6), were prepared and their thermal and mesomorphic properties investigated via differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FT-IR) in order to confirm their H-bonding interactions. The mesophase behavior of each mixture was examined by DSC and polarized optical microscopy (POM). According to the findings of the study, in all of the designed mixtures, the introduction of laterally polar chlorine atom to the supramolecular complexes produces polymorphic compounds possessing smectic A, smectic C and nematic mesophases, in addition, all products have low melting transitions. Thermal stabilities of the associated phases depend on the position and orientation of the lateral polar Cl- atom as well as the length of terminal flexible alkoxy chain. Comparisons were made between the present lateral Cl- complexes and previously investigated laterally-neat complexes in order to investigate the impact of the addition, nature and orientation of polar substituent on the mesomorphic behavior. The investigations revealed that, the polarity and mesomeric nature of inserted lateral substituent into the base component play an essential role in affecting their mesomorphic properties. Furthermore, for current complexes, induced polymorphic phases have been found by introducing the chlorine atom.

Investigation of Some Antiviral N-Heterocycles as COVID 19 Drug: Molecular Docking and DFT Calculations.

The novel coronavirus, COVID-19, caused by SARS-CoV-2, is a global health pandemic that started in December 2019. The effective drug target among coronaviruses is the main protease Mpro, because of its essential role in processing the polyproteins that are translated from the viral RNA. In this study, the bioactivity of some selected heterocyclic drugs named Favipiravir (1), Amodiaquine (2), 2'-Fluoro-2'-deoxycytidine (3), and Ribavirin (4) was evaluated as inhibitors and nucleotide analogues for COVID-19 using computational modeling strategies. The density functional theory (DFT) calculations were performed to estimate the thermal parameters, dipole moment, polarizability, and molecular electrostatic potential of the present drugs; additionally, Mulliken atomic charges of the drugs as well as the chemical reactivity descriptors were investigated. The nominated drugs were docked on SARS-CoV-2 main protease (PDB: 6LU7) to evaluate the binding affinity of these drugs. Besides, the computations data of DFT the docking simulation studies was predicted that the Amodiaquine (2) has the least binding energy (-7.77 Kcal/mol) and might serve as a good inhibitor to SARS-CoV-2 comparable with the approved medicines, hydroxychloroquine, and remdesivir which have binding affinity -6.06 and -4.96 Kcal/mol, respectively. The high binding affinity of 2 was attributed to the presence of three hydrogen bonds along with different hydrophobic interactions between the drug and the critical amino acids residues of the receptor. Finally, the estimated molecular electrostatic potential results by DFT were used to illustrate the molecular docking findings. The DFT calculations showed that drug 2 has the highest of lying HOMO, electrophilicity index, basicity, and dipole moment. All these parameters could share with different extent to significantly affect the binding affinity of these drugs with the active protein sites.

Chair- and V-Shaped of H-bonded Supramolecular Complexes of Azophenyl Nicotinate Derivatives; Mesomorphic and DFT Molecular Geometry Aspects.

New geometrical architectures of chair- and V-shaped supramolecular liquid crystalline complexes were molded through 1:1 intermolecular hydrogen bonding interactions between 4-(4-(hexyloxy)phenylazo)methyl)phenyl nicotinate and 4-alkoxybenzoic acids. The length of terminal alkoxy acid chains varied, n = 6 to 16 carbons. The mesomorphic behaviour of these complexes was examined through differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). Fourier-transform infrared spectroscopy (FT-IR) was carried out to confirm the presence of Fermi bands that appeared for the hydrogen bonding formation. Enantiotropic nematic phases were observed and covered all lengths of alkoxy chains. The geometrical structures of the prepared supramolecular complexes geometries were estimated by Density functional theory (DFT) calculations. The supramolecular complexes I/An are projected to exhibit a nonlinear geometry with V-shaped and chair-shaped geometry. The chair-shaped conformers of I/An were found to be more stable than V-shaped isomeric complexes. Moreover, the effect of the change of the mesogenic core on the mesophase thermal stability (TC) has been investigated by a comparative study of the present azo supramolecular H-bonding LCs (SMHBCs) I/An and our previously reported their Schiff base analogue complexes, II/An. The findings of the DFT illustrated the high impact of CH=N as a mesogenic core on the mesomorphic behavior in terms of the competitive lateral and terminal intermolecular interactions as well as the molecular electrostatic potential (MEP).