Remarkable Nonlinear Properties of a Novel Quinolidone Derivative: Joint Synthesis and Molecular Modeling.

A novel 4(1H) quinolinone derivative (QBCP) was synthesized and characterized with single crystal X-ray diffraction. Hirshfeld surfaces (HS) analyses were employed as a complementary tool to evaluate the crystal intermolecular interactions. The molecular global reactivity parameters of QBCP were studied using HOMO and LUMO energies. In addition, the molecular electrostatic potential (MEP) and the UV-Vis absorption and emission spectra were obtained and analyzed. The supermolecule (SM) approach was employed to build a bulk with 474,552 atoms to simulate the crystalline environment polarization effect on the asymmetric unit of the compound. The nonlinear optical properties were investigated using the density functional method (DFT/CAM-B3LYP) with the Pople's 6-311++G(d,p) basis set. The quantum DFT results of the linear polarizability, the average second-order hyperpolarizability and the third-order nonlinear susceptibility values were computed and analyzed. The results showed that the organic compound (QBCP) has great potential for application as a third-order nonlinear optical material.

Second-order nonlinear optical properties of two chalcone derivatives: insights from sum-over-states.

In this study, a combined experimental and theoretical study of the nonlinear optical properties (NLO) of two chalcone derivatives, (E)-3-(2-methoxyphenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (MPSP) and (E)-3-(3-nitrophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (NPSP), in DMSO is reported. The single crystal structures of the compounds, which differ only by the type and position of one substituent, were grown using the slow evaporation technique, and the main structural differences are discussed. The two-photon absorption and first-order hyperpolarizability measurements were performed via the Z-scan technique and hyper-Rayleigh scattering experiment in DMSO. The theoretical calculations were performed using the Density Functional Theory (DFT) at the CAM-B3LYP/6-311++G(d,p) level, and the sum-over-states (SOS) approach in both static and dynamic cases. Besides the electron conjugation achieved by the aromatic rings, olefins, and carbonyl groups, both compounds have a nearly flat chalcone backbone, which is believed to contribute to the nonlinear optical properties. MPSP and NPSP have different positions, even though they have roughly the same conformation and form C-HO interactions. For several studied frequencies, the HRS first hyperpolarizability values for MPSP are greater than those for NPSP, indicating that in most cases the NLO properties of MPSP are better. The comparison among the theoretical and experimental HRS first hyperpolarizability results showed a good agreement. In addition, the two-dimensional second order nonlinear optical spectra obtained from the sum-over-states model indicate good second-order NLO responses of the two chalcone derivatives under external fields. Our findings are important not only to show the potential nonlinear optical application of the two new compounds but also to gain an insight into how different chemical compositions might affect the crystal structures and physico-chemical properties.

Structural comparison of five new halogenated dihydroquinoline-4(1H)-ones.

Compounds with dihydroquinoline-4(1H)-one nuclei have been reported in the literature for being important in the development of medicines due to their broad spectrum of activities. In this way, the structural knowledge of this class becomes relevant for obtaining new materials with desired biological properties. This study presents the structural elucidation of five halogenated dihydroquinolines, as well as the discussion about the effect on the molecular conformation of the type and position of halogen atom on aromatic rings. Compounds I and IV differ in halogen substitution on 2-phenyl ring, while compounds III and V differ in halogen substitution on the benzylidene ring. Moreover, compound II has a para-substituted 2-phenyl ring in their molecular structure. The crystal packing of all five molecules is mainly ruled by C-H⋯O and C-H···halogen interactions that form dimers and chains. The shift in position and the kind of the halogen in ring C shows a starring role in the conformation of the studied compounds, and the packaging of these compounds is more susceptible to variations when the halogen position changes.

A new quinolinone-chalcone hybrid with potential antibacterial and herbicidal properties using in silico approaches.

Quinolinone-chalcones are hybrid compounds consisting of chalcone and quinolone moieties with biological activity related to their hybrid structure. This work seeks to describe the structural and theoretical parameters related to the physicochemical properties and biological activity of a new quinolinone-chalcone. The synthesis, structural characterization by X-ray diffraction, molecular topology by Hirshfeld surfaces and QTAIM, molecular electronic calculations, and pharmacophore analysis were described. The weak interactions C-H…O, C-H…π, and C-H…Br were responsible for crystal growth and stabilized the crystalline state. The DFT analysis shows that the sulfonamide group region is susceptible to observed interactions, and the frontier molecular orbitals indicate high kinetic stability. Also, pharmacophore analysis revealed potential antibacterial and herbicidal activity; by docking within the active site of TtgR, a transcription regulator for the efflux pump TtgABC from the highly resistant Pseudomonas putida (P. putida) strain DOT-TIE, we showed that the activation of TtgR relies upon the binding of aromatic-harboring compounds, which plays a crucial role in bacterial evasion. In this context, a new quinolinone-chalcone has a higher binding affinity than tetracycline, which suggests it might be a better effector for TtgR.

Insights on a new sulfonamide chalcone with potential antineoplastic application.

Chalcones (E)-1,3-diphenyl-2-propene-1-ones, a class of biosynthetic precursor molecules of flavonoids, have a wide variety of biological applications. Besides the natural products, many synthetic derivatives and analogs became an object of continued interest in academia and industry. In this work, a synthesis and an extensive structural study were performed on a sulfonamide chalcone 1-Benzenesulfonyl-3-(4-bromobenzylidene)-2-(2-chlorophenyl)-2,3-dihydro-1H-quinolin-4-one with potential antineoplastic application. In addition, in silico experiments have shown that the sulfonamide chalcone fits well in the ligand-binding site of EGFR with seven µ-alkyl binding energy interactions on the ligand-binding site. Finally, the kinetic stability and the pharmacophoric analysis for EGFR indicated the necessary spatial characteristics for potential activity of sulfonamide chalcone as an antagonist.

Development and Analytical Validation of the Methodology for Vitamins in Tablets by Ultra-Performance Liquid Chromatography.

In the present study, we developed a reliable and robust chromatographic method for the quantification of multivitamins in tablet samples by ultra-performance liquid chromatography (UPLC) with photodiode array detection. The vitamins nicotinamide, pyridoxine, riboflavin, and thiamin were analyzed and quantified in a total analysis time of 2.5 minutes, using hydrophilic interaction liquid chromatography stationary phase. Tocopherol acetate and cyanocobalamin were analyzed and quantified in a total analysis time of 2.5 minutes, using reversed-phase (RP)-UPLC. The analysis time reported here is lower than that of similar methods reported in the literature for single vitamin determination. The method linearity exhibits a good correlation coefficient (R2 = 0.998) with the relative residual standard deviation in the acceptable limit of 2.0%. The developed methods were validated, and the results demonstrated that the proposed analytical method showed to be selective, sensitive, accurate, and robust for the quantification of evaluated vitamins in multivitamin tablets. The work was fully developed in the quality control laboratory of a pharmaceutical industry in the Agroindustrial District of Anápolis (DAIA, Goiás, Brazil), where the product is manufactured.

Analysis of two novel 1-4 quinolinone structures with bromine and nitrobenzyl ligands.

The scientific community has shown particular interest in the study of quinolinones-a class of bicyclic organic compounds. An example of these compounds are the 4-quinolinones, considered to be very useful building blocks, since they can adapt their molecular structures with different ligands for applications in various fields such as pharmacy, medicine, physics and engineering. The compounds (E)-3-(benzylidene)-2-(3-nitrophenyl)-2,3-dihydro-1-(phenylsulfonyl)-quinolin-4-(1H)-one (NFQ) and (E)-3-(benzylidene)-2-(4-bromophenyl)-2,3-dihydro-1-(phenylsulfonyl) quinolin-4-(1H)-one (BFQ) were synthesized and characterized by infrared spectroscopy, 1H and 13C NMR, and melting point. NFQ crystallized in the orthorhombic Pbca space group while BFQ appears in the monoclinic P21/n space group. X-ray diffraction was used to evaluate their crystallographic structures, and Hirshfeld surface evaluates the intermolecular interactions, supramolecular arrangement and packaging. Theoretical vibrational assignments and calculated electronic properties also demonstrate acceptable agreement between experimental and theoretical results.

ss-NMR and single-crystal X-ray diffraction in the elucidation of a new polymorph of bischalcone (1E,4E)-1,5-bis(4-fluorophenyl)penta-1,4-dien-3-one.

We report a new polymorph of (1E,4E)-1,5-bis(4-fluorophenyl)penta-1,4-dien-3-one, C17H12F2O. Contrary to the precedent literature polymorph with Z' = 3, our polymorph has one half molecule in the asymmetric unit disordered over two 50% occupancy sites. Each site corresponds to one conformation around the single bond vicinal to the carbonyl group (so-called anti or syn). The other half of the bischalcone is generated by twofold rotation symmetry, giving rise to two half-occupied and overlapping molecules presenting both anti and syn conformations in their open chain. Such a disorder allows for distinct patterns of intermolecular C-H...O contacts involving the carbonyl and anti-oriented ß-C-H groups, which is reflected in three 13C NMR chemical shifts for the carbonyl C atom. Here, we have also assessed the cytotoxicity of three symmetric bischalcones through their in vitro antitumour potential against three cancer cell lines. Cytotoxicity assays revealed that this biological property increases as halogen electronegativity increases.