3383-83-3Relevant articles and documents
Synthesis and Characterization of Near-Infrared Emissive Chiral π-Conjugated Polymers Incorporating Perylenyl Moieties with Visible-Light Absorption
Li, Junfeng,Chen, Ying,Yang, Chenglong,Lai, Wen-Yong
, p. 2451 - 2456 (2015)
A novel set of multifunctional optically active π-conjugated polymers incorporating perylenyl moieties, were designed and synthesized. Chirality transfer and amplification from chiral unit to the main-chain backbone in dilute solution was achieved, which was closely related to the stereocenter in the pendant of a π-conjugated polymer. In addition, annealed films of these polymers exhibited near-infrared emission by direct absorption of visible light, resulting from the introduction of a strong fluorophore perylenyl moiety. Such a design strategy opens up new perspectives for the future development of novel optically active materials with near-infrared emission for photonic applications.
Thermodynamic Characterization of Surface and Solubility of 5-((S)-3,7-Dimethyloctyloxy)-2-[[[4-(octyloxy)phenyl]imino]methyl]phenol Liquid Crystal with Some Solvents
Mutlu Yanic, Serap,Cakar, Fatih,Ocak, Hale,Karaman, Ferdane,Cankurtaran, Ozlem,Bilgin Eran, Belklz
, p. 1007 - 1013 (2019)
The inverse gas chromatography method was used to obtain dispersive surface energy, surface acidity or basicity constants, mole fraction activity coefficients of the solvents at infinite dilution for a new salicylaldimine based chiral calamitic liquid crystal 5-((S)-3,7-dimethyloctyloxy)-2-[[[4-(octyloxy)phenyl]imino]methyl]phenol (DOPIMP). The dispersive surface energy of DOPIMP was estimated as 41.1 mJ/m2 at 30 °C and decreased with temperature. The specific free energy, enthalpy, and entropy of adsorption of the selected polar solvents on the liquid crystal were determined. The values of adsorption enthalpy were correlated with both donor and acceptor numbers of the solvents to quantify acidic KA and basic KD parameters of the liquid crystal surface. The results indicated that the surface of DOPIMP is basic. The retention diagrams of n-hexane, n-heptane, n-octane, n-nonane, n-decane, undecane, ethyl acetate, n-butyl acetate, iso-butyl acetate, toluene, ethylbenzene, n-propylbenzene, and chlorobenzene on the DOPIMP were plotted as straight lines using the net retention volumes at temperatures between 368.2 and 398.2 K. The values of activity coefficients indicated that DOPIMP was better soluble in long chain alkanes. Negatively signed partial molar Gibbs energies of mixing were obtained at infinite dilution of studied solvents.
Light-driven supramolecular chirality in propeller-like hydrogen-bonded complexes that show columnar mesomorphism
Vera, Francisco,Tejedor, Rosa M.,Romero, Pilar,Barbera, Joaquin,Ros, M. Blanca,Serrano, Jose Luis,Sierra, Teresa
, p. 1873 - 1877 (2007)
(Graph Presented) Shine a light! Columnar mesomorphic assembles of propeller-like hydrogen-bonded complexes show a chiral photo-response upon irradiation with circularly polarized light (CPL) of a given handedness (see picture). The materials can behave as a supramolecular switch that undergoes helix inversion when irradiated with the oppositely polarized light.
A supramolecular helix that disregards chirality
Roche, Cécile,Sun, Hao-Jan,Leowanawat, Pawaret,Araoka, Fumito,Partridge, Benjamin E.,Peterca, Mihai,Wilson, Daniela A.,Prendergast, Margaret E.,Heiney, Paul A.,Graf, Robert,Spiess, Hans W.,Zeng, Xiangbing,Ungar, Goran,Percec, Virgil
, p. 80 - 89 (2016)
The functions of complex crystalline systems derived from supramolecular biological and non-biological assemblies typically emerge from homochiral programmed primary structures via first principles involving secondary, tertiary and quaternary structures. In contrast, heterochiral and racemic compounds yield disordered crystals, amorphous solids or liquids. Here, we report the self-assembly of perylene bisimide derivatives in a supramolecular helix that in turn self-organizes in columnar hexagonal crystalline domains regardless of the enantiomeric purity of the perylene bisimide. We show that both homochiral and racemic perylene bisimide compounds, including a mixture of 21 diastereomers that cannot be deracemized at the molecular level, self-organize to form single-handed helical assemblies with identical single-crystal-like order. We propose that this high crystalline order is generated via a cogwheel mechanism that disregards the chirality of the self-assembling building blocks. We anticipate that this mechanism will facilitate access to previously inaccessible complex crystalline systems from racemic and homochiral building blocks.
Synthesis, preparation, and characterization of liquid crystal/organo-montmorillonite nanocomposites
Yanic, Serap Mutlu,Guzeller, Dilek,Ocak, Hale,Cakar, Fatih,Erol, Ismail,Cankurtaran, Ozlem,Eran, Belkis Bilgin
, p. 23 - 31 (2015)
A new chiral calamitic liquid crystal 4′-((S)-3,7-dimethyloctyloxy)phenyl 4-(10-undecen-1-yloxy)benzoate (DOPUB) has been synthesized and characterized by spectroscopic methods (1H-NMR and 13C-NMR). The focus is on the preparation of the nanocomposites of new chiral calamitic liquid crystal DOPUB/Organo-montmorillonite clay (OMMT) by solution intercalation method addition with OMMT contents 2.5, 5, and 7.5 wt% and determination of the morphology, thermal behavior, and crystalline properties of liquid crystal DOPUB/OMMT. Montmorillonite (MMT) modified by cationic surfactant cetyltrimethylammonium bromide (CTAB) for increasing the interaction of clay with DOPUB liquid crystal. The characterization of clay minerals and nanocomposites was investigated by X-ray diffraction. The mesomorphic behavior of liquid crystal (DOPUB) and the nanocomposites was investigated by differential scanning calorimetry (DSC) and optical polarizing microscopy (PM).
A study of the thermodynamical interactions with solvents and surface characterisation of liquid crystalline 5-((S)-3,7-dimethyloctyloxy)-2-[[[4-(dodecyloxy)phenyl]imino]-methyl]phenol by inverse gas chromatography
Ocak, Hale,Mutlu-Yanic, Serap,Cakar, Fatih,Bilgin-Eran, Belkis,Guzeller, Dilek,Karaman, Ferdane,Cankurtaran, Ozlem
, p. 861 - 867 (2016)
An inverse gas chromatography (IGC) study of thermodynamic interactions of a new chiral calamitic liquid crystalline 5-((S)-3,7-Dimethyloctyloxy)-2-[[[4-(dodecyloxy)phenyl]imino]methyl]phenol (DODPIMP) with some solvents was presented. The retention diagrams of the solvents on the DODPIMP were plotted by specific retention volumes, Vg0 at temperatures between 373.2 and 393.2?K. The Flory-Huggins interaction parameter, χ12∞, the weight fraction activity coefficient, Ω1∞ and selectivity coefficients, α, of the structural isomers were determined for the DODPIMP liquid crystal. To characterize the surface properties of, retention diagrams of several non-polar and polar solvents on the DODPIMP were plotted by net retention volumes, VN in the temperature range from 303.2 to 318.2?K. The dispersive surface energy, the thermodynamic adsorption parameters and the acid–base constants of the compound in the crystalline phase were determined. The results indicated a basic character for the surface of DODPIMP at the studied conditions.
Large Faraday Rotation in Optical-Quality Phthalocyanine and Porphyrin Thin Films
Nelson, Zachary,Delage-Laurin, Leo,Peeks, Martin D.,Swager, Timothy M.
supporting information, p. 7096 - 7103 (2021/05/29)
The magneto-optical phenomenon known as Faraday rotation involves the rotation of plane-polarized light as it passes through an optical medium in the presence of an external magnetic field oriented parallel to the direction of light propagation. Faraday rotators find applications in optical isolators and magnetic-field imaging technologies. In recent years, organic thin films comprised of polymeric and small-molecule chromophores have demonstrated Verdet constants, which measure the magnitude of rotation at a given magnetic field strength and material thickness, that exceed those found in conventional inorganic crystals. We report herein the thin-film magnetic circular birefringence (MCB) spectra and maximum Verdet constants of several commercially available and newly synthesized phthalocyanine and porphyrin derivatives. Five of these species achieved maximum Verdet constant magnitudes greater than 105 deg T-1 m-1 at wavelengths between 530 and 800 nm. Notably, a newly reported zinc(II) phthalocyanine derivative (ZnPc-OT) reached a Verdet constant of -33 × 104 deg T-1 m-1 at 800 nm, which is among the largest reported for an organic material, especially for an optical-quality thin film. The MCB spectra are consistent with resonance-enhanced Faraday rotation in the region of the Q-band electronic transition common to porphyrin and phthalocyanine derivatives, and the Faraday A-term describes the electronic origin of the magneto-optical activity. Overall, we demonstrate that phthalocyanines and porphyrins are a class of rationally designed magneto-optical materials suitable for applications demanding large Verdet constants and high optical quality.
The synthesis and dielectric properties of a new phenylbenzoate-based calamitic liquid crystal
Ahlatc?o?lu ?zerol, Esma,Ocak, Hale,Bilgin Eran, Belk?z,Karavelio?lu, Selvi
, p. 225 - 232 (2020/08/10)
The dielectric investigation has a great importance in liquid crystal studies as a supportive method to DSC for a complete characterization of liquid crystals as well as in the electronic applications. In this study, the synthesis, mesomorphic characterization and dielectric properties of a new phenylbenzoate-based three-ring calamitic liquid crystal which composed of ester linking groups, (S)-3,7-dimethyloctyloxy chiral unit at one of terminals and n-octyloxy chain at the other end of the molecule, have been reported. The new calamitic liquid crystal 4-[4-((S)-3,7-dimethyloctyloxy)phenoxy)carbonyl]phenyl 4-(n-octyloxy)benzoate (DPCPB) has been characterized using 1H, 13C-NMR and MS-QTOF. The liquid crystalline behavior of the target compound has been investigated by differential scanning calorimetry and optical polarizing microscopy. DPCPB exhibits an enantiotropic non-tilted smectic mesophase in a wide temperature range. The real and imaginary dielectric constant, conductivity mechanism, impedance and dielectric relaxation mechanism of DPCPB have been investigated depending on frequency at different temperatures.
Extraordinary magnetic field effects on the LC phases of homochiral and racemic 4-cyanoresorcinol-based diamagnetic bent-core mesogens
Ocak, Hale,Bilgin Eran, Belk?z,Nuray, Sevgi,?zkonstanyan, Aykun,Poppe, Silvio,Tschierske, Carsten
, p. 1895 - 1910 (2021/03/01)
4-Cyanoresorcinol based bent-core compounds combining one branched chiral with one achiral linear end-chain have been synthesized in enatiomerically pure and one compound also in racemic form. All homochiral compounds form a chiral cybotactic nematic phase at relatively low temperature with a selective reflection ranging from the near IR to near UV. For the compound with the longest chains superparaelectric and antiferroelectric switching smectic phases were observed, whereas the corresponding racemate is non-polar. This is attributed to sterically induced polarization by the denser packing of uniform enantiomers due to chirality synchronization of the helical conformers. For the racemic mixture this chirality synchronization requires additional surface stabilization. There are unprecedented effects of an applied magnetic field (1 T) on the LC phases, leading to a layer shrinkage by 6-13% for the enantiomer and a layer expansion by 5-8% for the racemate. It is proposed that the magnetic field couples with the π-systems of the almost rod-like molecules. For the racemate this increases the core order, whereas for the enantiomer the reduction of the heliconical twist is considered to provide the major effect. These magnetic field effects could lead to new applications of chiral LC materials at the cross-over between rod-like and bent shapes.
Novel tdp1 inhibitors based on adamantane connected with monoterpene moieties via heterocyclic fragments
Chepanova, Arina A.,Dyrkheeva, Nadezhda S.,Ilina, Ekaterina S.,Korchagina, Dina V.,Lavrik, Olga I.,Mozhaitsev, Evgenii S.,Munkuev, Aldar A.,Reynisson, Jóhannes,Salakhutdinov, Nariman F.,Suslov, Evgeniy V.,Volcho, Konstantin P.,Zakharenko, Alexandra L.,Zakharova, Olga D.
, (2021/06/12)
Tyrosyl-DNA phosphodiesterase 1 (Tdp1) is a promising target for anticancer therapy due to its ability to counter the effects topoisomerase 1 (Top1) poison, such as topotecan, thus, decreasing their efficacy. Compounds containing adamantane and monoterpenoid residues connected via 1,2,4-triazole or 1,3,4-thiadiazole linkers were synthesized and tested against Tdp1. All the derivatives exhibited inhibition at low micromolar or nanomolar concentrations with the most potent inhibitors having IC50 values in the 0.35–0.57 μM range. The cytotoxicity was determined in the HeLa, HCT-116 and SW837 cancer cell lines; moderate CC50 (μM) values were seen from the mid-teens to no effect at 100 μM. Furthermore, citral derivative 20c, α-pinene-derived compounds 20f, 20g and 25c, and the citronellic acid derivative 25b were found to have a sensitizing effect in conjunction with topotecan in the HeLa cervical cancer and colon adenocarcinoma HCT-116 cell lines. The ligands are predicted to bind in the catalytic pocket of Tdp1 and have favorable physicochemical properties for further development as a potential adjunct therapy with Top1 poisons.
