Studies in crystal engineering: Crystal packing, topological photodimerization and structure-reactivity correlations in fluoro-substituted styrylcoumarins

In continuation of our studies on the influence of fluoro substitution on the solid state photobehaviour and packing pattern of styrylcoumarins, the results obtained for 4-(3-fluorostyryl)coumarin 1, 4-styryl-6-fluorocoumarin 2 and 4-styryl-7-fluorocoumarin 3 are presented. The configuration of the dimers was established on the basis of crystal packing of 1 and 2 (alpha-packed). A rationale for the significantly lower dimer yield in the crystal for 2 is proposed. In the observed centrosymmetric arrangement of the reactants the C=O ...pi (phenyl) contacts seem to provide additional attractive interactions. C-H ... O and C-H ... F hydrogen bonding seems to provide stability in these structures.

Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching

Triplet lifetimes have been determined for the diastereomers of a broad set of butane-l,4-dione derivatives (1-3). A remarkable dependence of lifetimes on conformational preferences is revealed in that the lifetimes are shorter for the meso diastereomers of 1-3 than those for the racemic ones. The intramolecular beta-phenyl quenching is promoted in the case of meso diastereomers by virtue of the gauche relationship between the excited carbonyl group and the beta-aryl ring, while a distal arrangement in the lowest energy conformation (H-anti) in racemic diastereomers prevents such a deactivation. The involvement of charge transfer in the intramolecular beta-phenyl quenching is suggested by the correlation of the triplet lifetimes of the meso diastereomers of compounds 2 with the nature of the substituent on the beta-phenyl rings. In the case of racemic diastereomers, beta-methoxy substitution on the beta-phenyl ring (2-OCH3, 3-OCH3) also led to a decrease of the triplet lifetimes when compared to those of the nonsubstituted compounds (2-H, 3-H). This shortening is accounted for by the deactivation of a small proportion of the excited molecules through beta-phenyl quenching. In addition to the above factors, the lifetimes in the case of meso diastereomers can further be controlled by increasing the energy spacing between the T-1 and T-2 states, since beta-phenyl quenching occurs from the latter for compounds 2 and 3. Through a rational conformational control, a surprisingly long triplet lifetime (300 ns) has been measured for the first time for a purely n,pi* triplet-excited beta-phenylpropiophenone dimer (1-rac).

Studies on strontium substituted rare earth manganites

Sintering, electrical conductivity and thermal expansion behaviour of combustion synthesised strontium substituted rare earth manganites with the general formula Ln(1-x)Sr(x)MnO(3) (Ln = Pr, Nd and Sm; x = 0, 0.16 and 0.25) have been investigated as solid oxide fuel cell cathode materials. The combustion derived rare earth manganites have surface area in the range of 13-40 m(2)/g. Strontium substitution increases the electrical conductivity values in all the rare earth manganites. With the decreasing ionic radii of rare earth ions, the conductivity value decreases. Among the rare earth manganites studied, (Pr/Nd)(0.75)Sr0.25MnO3 show high electrical conductivity ( > 100 S/cm). The thermal expansion coefficients of Pr0.75Sr0.25MnO3 and Nd0.75Sr0.25MnO3 were found to be 10.2 x 10(-6) and 10.7 x 10(-6) K-1 respectively, which is very close to that of the electrolyte (YSZ) used in solid oxide fuel cells. (C) 1999 Elsevier Science B.V. All rights reserved.

Thermal degradation studies of para-substituted poly(styrene peroxide)s

The thermal degradation of a series of para-substituted poly(styrene peroxide)s with electron-donating [CH3, C(CH3)(3)] and electron-attracting (Br) substitutents are investigated by thermogravimetric analysis (TGA). The results indicate that the Hammett relationship can describe quantitatively the trends in maximum rate of polymer decomposition (T-max) observed in TGA and thus thermostability of substituted poly(styrene peroxide)s depends only on the electronic nature of substituents and their ability to stabilize macroradicals formed during chain scission. The experimental results are also substantiated by thermochemical calculations. (C) 2002 Elsevier Science Ltd. All rights reserved.

Reactivity switching and selective activation of C-1 or C-3 in 2,3-unsaturated thioglycosides

Reactivity switching and selective activation of C-1 or C-3 in 2,3-unsaturated thioglycosides, namely, 2,3-dideoxy-1-thio-D-hex-2-enopyranosides are reported. The reactivity switching allowed activation of either C-1 or C-3, with the use of either N-iodosuccinimide (NIS)/triflic acid (TfOH) or TfOH alone. C-1 glycosylation with alcohol acceptors occurred in the presence of NIS/TfOH, without the acceptors reacting at C-3. On the other hand, reaction of 2,3-unsaturated thioglycosides with alcohols mediated by triflic acid led to transposition of C-1 ethylthio-moiety to C-3 intramolecularly, to form 3-ethylthio-glycals. Resulting glycals underwent glycosylation with alcohols to afford 3-ethylthio-2-deoxy glycosides. However, when thiol was used as an acceptor, only a stereoselective addition at C-3 resulted, so as to form C-1, C-3 dithio-substituted 2-deoxypyranosides. (C) 2011 Elsevier Ltd. All rights reserved.

Synthesis and Antileukemic Activity of Novel 4-(3-(Piperidin-4-yl) Propyl)Piperidine Derivatives

To explore the anticancer effect associated with the piperidine framework, several (substituted phenyl) {4-[3-(piperidin-4-yl)propyl]piperidin-1-yl} methanone derivatives 3(a-i) were synthesized. Variation in the functional group at N-terminal of the piperidine led to a set of compounds bearing amide moiety. Their chemical structures were confirmed by (1)H NMR, IR and mass spectra analysis. Among these, compounds 3a, 3d and 3e were endowed with antiproliferative activity. The most active compound among this series was 3a with nitro and fluoro substitution on the phenyl ring of aryl carboxamide moiety, which inhibited the growth of human leukemia cells (K562 and Reh) at low concentration. Comparison with other derivative (3h) results shown by LDH assay, cell cycle analysis and DNA fragmentation suggested that 3a is more potent to induce apoptosis.

Structural, dielectric relaxation and piezoelectric characterization of Sr2+ substituted modified PMS-PZT ceramic

Pyrochlore phase free [Pb0.94Sr0.06] [(Mn1/3Sb2/3)(0.05)(Zr0.53Ti0.47)(0.95)] O-3 ceramics has been synthesized with pure Perovskite phase by semi-wet route using the columbite precursor method. The field dependences of the dielectric response and the conductivity have been measured in a frequency range from 50 Hz to 1 MHz and in a temperature range from 303 K to 773 K. An analysis of the real and imaginary parts of the dielectric permittivity with frequency has been performed, assuming a distribution of relaxation times. The scaling behavior of the dielectric loss spectra suggests that the distribution of the relaxation times is temperature independent. The SEM photographs of the sintered specimens present the homogenous structures and well-grown grains with a sharp grain boundary. The material exhibits tetragonal structure. When measured at frequency (100 Hz), the polarization shows a strong field dependence. Different piezoelectric figures of merit (k(p), d(33) and Q(m)) of the material have also been measured obtaining their values as 0.53, 271 pC/N and 1115, respectively, which are even higher than those of pure PZT with morphotropic phase boundary (MPB) composition. Thus the present ceramics have the optimal overall performance and are promising candidates for the various high power piezoelectric applications. (C) 2011 Elsevier B.V. All rights reserved.

Evaluation of DNA binding, antioxidant and cytotoxic activity of mononuclear Co(III) complexes of 2-oxo-1,2-dihydrobenzoh]quinoline-3-carbaldehyde thiosemicarbazones

Four new 2-oxo-1,2-dihydrobenzoh]quinoline-3-carbaldehyde N-substituted thiosemicarbazone ligands (H-2-LR, where R = H, Me, Et or Ph) and their corresponding new cobalt(III) complexes have been synthesized and characterized. The structures of the complexes 2 and 3 were determined by single crystal X-ray diffraction analysis. The interactions of the new complexes with DNA were investigated by absorption, emission and viscosity studies which indicated that the complexes bind to DNA via intercalation. Antioxidant studies of the new complexes showed that the significant antioxidant activity against DPPH radical. In addition, the in vitro cytotoxicity of complexes 1-4 against A549 cell line was assayed which showed higher cytotoxic activity with lower IC50 values indicating their efficiency in killing the cancer cells even at very low concentrations. (C) 2012 Elsevier Masson SAS. All rights reserved.

Synthesis and an Evaluation of Molecular Conformation and Crystal Packing in Two Substituted 4-Phenylquinolines

The title compounds, namely Methyl 2-methyl-4 -phenylquinoline-3-carboxylate (I), C18H15NO2, and (2E)-3-(3,4-dimethoxyphenyl)-1-(2-methyl-4 -phenylquinolin-3-yl)prop-2-en-1-one (II), C27H23NO3, comprising of the phenyl ring, exhibit differences in conformational behaviour with respect to the plane of the quinoline fragment. (I) contains the methyl ester moiety whereas (II) contains the chalcone fragment, consisting of a double bond and phenyl group containing dimethoxy groups as substituents. The dihedral angles between the phenyl group and the quinoline ring is 82.77 (7)A degrees in (I), and 79.02 (8)A degrees in (II) respectively. It is the weak C-H center dot center dot center dot O=C H-bond and C-H center dot center dot center dot pi interactions which dictate packing of molecules in (I). In (II), it is C-H center dot center dot center dot N and C-H center dot center dot center dot pi, involving the dimethoxy ring, which controls packing of molecules in the crystal lattice. In addition, pi center dot center dot center dot pi aromatic stacking interactions involving the quinoline fragment is present in all the molecules. The title compounds, namely methyl-2-methyl-4 -phenylquinoline-3-carboxylate (I), C18H15NO2, and (2E)-3-(3,4-dimethoxyphenyl)-1-(2-methyl-4 -phenylquinolin-3-yl)prop-2-en-1-one (II), C27H23NO3, comprising of the phenyl ring, exhibit differences in conformational behaviour with respect to the plane of the quinoline fragment. (I) contains the methyl ester moiety whereas (III) contains the chalcone fragment, consisting of a double bond and phenyl group containing dimethoxy groups as substituents. The dihedral angles between the phenyl group and the quinoline ring is 82.77 (7)A degrees in (I), and 79.02 (8)A degrees in (II) respectively. It is the weak C-H center dot center dot center dot O=C H-bond and C-H center dot center dot center dot pi interactions which dictate packing of molecules in (I). In (II), it is C-H center dot center dot center dot N and C-H center dot center dot center dot pi, involving the dimethoxy ring, which controls packing of molecules in the crystal lattice. In addition, pi center dot center dot center dot pi aromatic stacking interactions involving the quinoline fragment is present in all the molecules.

Catalytic Asymmetric Synthesis of alpha,beta-Disubstituted alpha,gamma-Diaminophosphonic Acid Precursors by Michael Addition of alpha-Substituted Nitrophosphonates to Nitroolefins

Michael additions of alpha-substituted nitrophosphonates to various nitroolefins are shown to proceed with high diastereo- and enantioselectivity when catalyzed by a quinine-derived thiourea-tertiary amine bifunctional catalyst and generate alpha,gamma-diaminophosphonic acid precursors with contiguous quaternary and tertiary stereocenters.

Diaminotriazine substituted diphenyl ether: reversible structural transformation and solvent dependent solid state fluorescence

The effect of molecular shape and position of hydrogen bonding functionality in the solid state structural self-assembly was investigated using diaminotriazine substituted diphenyl ether based positional isomers (1-5). The molecular shape was modulated by changing diaminotriazine position that produced channel supramolecular structures in 1, 3 and 5. There exists a direct correlation between the molecular shape and three dimensional structures; more linear molecules resulted in close-packing whereas molecules with a labyrinthine topology formed a channel structure. Supramolecular aspects pertaining to the influence of solvent of crystallization in structure formation and reversible structural transformation in solid state were also explored. 1-5 exhibited tunable solid state fluorescence (lambda(max) = 437-496 nm) depending on the diaminotriazine substitutional position and 3 showed solvent-dependent solid state fluorescence. The present study describes the generation of a supramolecular channel structure with functional properties such as tunable fluorescence by varying the position of hydrogen bond functionality and solvent of crystallization.

Synthesis, Antioxidant, and Cytotoxic Activities of N-Azole Substituted Thiomorpholine Derivatives

A new class of N-azole substituted thiomorpholine derivatives were prepared and their antioxidant and cytotoxic activities were studied. The methyl substituted oxazolyl thiomorpholine dioxide 9b exhibited radical scavenging activity greater than the standard ascorbic acid. On the other hand, the thiazolyl thiomorpholine 10c having a chloro substituent on the aromatic ring was identified as a remarkable lead molecule for cytotoxic activity against A549 and HeLa cells, with IC50 values of 10.1 and 30.0 mu M, respectively.

Dicyanovinyl substituted triarylboranes: a rational approach to distinguish fluoride and cyanide ions

Two new dicyanovinyl (DCV) functionalized triarylboranes (Mes(2)B-pi-spacer-DCV, for 1: pi-spacer = C6H4, for 2: pi-spacer = 2,3,5,6-tetramethyl-phenyl) are reported. The molecular structures of 1 and 2 are similar except for the spacer which connects the boryl and DCV units. This small structural perturbation induces drastic changes in the optical properties of 1 and 2. Compound 2 shows weak dual fluorescence emission in nonpolar solvents and a stronger emission in polar solvents. Compound 1 is weakly fluorescent in polar environments but shows an intense single luminescence peak in less polar environments. Compound 1 exhibits a turn-off fluorescence response for both fluoride and cyanide: in contrast, 2 shows a turn on fluorescence response for both anions with different fluorescence signatures. The NMR titration studies reveal that for compound 2, fluoride binds to the boron centre and cyanide binds to the DCV unit. For compound 1, the fluoride ion binds to the boron center, whereas the CN- binds to both the Ar3B and DCV units.

Synthesis and antiproliferative activity of imidazo2,1-b]1,3,4]thiadiazole derivatives

A series of 2,5,6-substituted imidazo2,1-b]1,3,4]thiadiazole derivatives have been prepared and were tested for antiproliferative activity on cancer cells at the National Cancer Institute. Results showed that molecules with a benzyl group at position 2, exhibited an increase in activity for the introduction of a formyl group at the 5 position. The compound 2-benzyl-5-formyl-6-(4-bromophenyl)imidazo 2,1-b]1,3,4]thiadiazole 22 has been chosen for understanding the mechanism of action by various molecular and cellular biology studies. Results obtained from cell cycle evaluation analysis, analysis of mitochondrial membrane potential and Annexin V-FITC by flow cytometric analysis, ROS production and expression of apoptotic and DNA-repair proteins suggested that compound 22 induced cytotoxicity by activating extrinsic pathway of apoptosis, however, without affecting cell cycle progression. (C) 2014 Elsevier Ltd. All rights reserved.

Catalytic Asymmetric Michael Addition/Cyclization Cascade Reaction of 3-Isothiocyanatooxindoles with Nitro Olefins

The first organocatalytic asymmetric reaction of 3-isothiocyanatooxindoles with nitro olefins has been developed by using a cinchonidine-derived bifunctional catalyst. The resulting products, highly functionalized 3,2-pyrrolidinyl-substituted spirooxindole derivatives, were obtained in high yields with good diastereo- and enantioselectivities (up to dr >20:1 and er = 96:4). This Michael addition/cyclization cascade reaction employs monosubstituted nitro olefins and complements the Zn-II-catalyzed variant, which is only applicable to disubstituted nitro olefins.