4-{2-[4-(Dimethylamino)phenyl]ethylidene}benzonitrile

In the crystal of the title compound, C(17)H(16)N(2), molecules are linked by C-H center dot center dot center dot N hydrogen bonds, forming rings of graph-set motifs R(2)(1) (6) and R(2)(2) (10). The title molecule is close to planar, with a dihedral angle between the aromatic rings of 0.6 (1)degrees. Torsion angles confirm a conformational trans structure.

Redetermination of 1-benzyl-3-furoyl-1-phenylthiourea

The title compound, C(19)H(16)N(2)O(2)S, was synthesized from furoyl isothiocyanate and N-benzylaniline in dry acetone and the structure redetermined. The structure [Otazo-Sanchez et al. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 2211-2218] has been re-determined in order to establish the intramolecular and intermolecular interactions. The thiourea group is in the thioamide form. The thiourea group makes a dihedral angle of 29.2 (6)degrees with the furoyl group. In the crystal structure, molecules are linked by intermolecular C-H center dot center dot center dot O interactions, forming one-dimensional chains along the a axis. An intramolecular N-H center dot center dot center dot O hydrogen bond is also present.

N-(4-chlorophenyl)maleimide

In the title compound, C10H6ClNO2, the dihedral angle between the benzene and maleimide rings is 47.54 (9)degrees. Molecules form centrosymmetric dimers through C-H center dot center dot center dot O hydrogen bonds, resulting in rings of graph- set motif R2 2(8) and chains in the [100] direction. Molecules are also linked by C-H center dot center dot center dot Cl hydrogen bonds along [001]. In this same direction, molecules are connected to other neighbouring molecules by C-H center dot center dot center dot O hydrogen bonds, forming edge- fused R-4(4)(24) rings.

1-(o-tolyl)thiourea

In the title compound, C(8)H(10)N(2)S, the o-tolyl group and the thiourea core are planar. The mean planes of the two groups are almost perpendicular [82.19 (8)degrees]. The thiourea group is in the thioamide form, in which resonance is present. In the crystal structure, molecules are linked by intermolecular N-H center dot center dot center dot S hydrogen bonds, forming two infinite chains parallel to the (110) and (110) planes.

N-(2-furylcarbonyl)piperidine-1-carbothioamide

The title compound, C11H14N2O2S, was synthesized from furoyl isothiocyanate and piperidine in dry acetone. The thiourea group is in the thioamide form. The thiourea group makes a dihedral angle of 53.9 (1)degrees with the furan carbonyl group. In the crystal structure, molecules are linked by intermolecular N-H center dot center dot center dot O hydrogen bonds, forming one-dimensional chains along the c axis. An intramolecular N-H center dot center dot center dot O hydrogen bond is also present.

Hydrogen bonding in 2-(2-oxothiazolidin-3-yl)-4,5-dihydrothiazolium hydrogen sulfate monohydrate

The asymmetric unit of the title compound, C(6)H(9)N(2)OS(2)(+)center dot-HSO(4)(-)center dot H(2)O, contains a heterocyclic cation, a hydrogen sulfate anion and a water molecule. There are strong hydrogen bonds between the hydrogen sulfate anions and water molecules, forming an infinite chain along the [010] direction, from which the cations are pendent. The steric, electronic and geometric features are compared with those of similar compounds. In this way, structural relationships are stated in terms of the influence of the sulfate group on the protonation of the heterocycle and on the tautomeric equilibrium in the solid state.

Antiferromagnetism with spin polarization of GaN-based diluted magnetic semiconductors

The diluted magnetic semiconductors are promising materials for spintronic applications. Usually one intents to find the ferromagnetic state but recently the antiferromagnetism (AFM) was proposed to have some advantages. In this work, we verify the possibility to obtain spin polarization with an AFM state. In particular, we studied GaN 5% double doped with two different transition metals atoms (Mn and Co or Cr and Ni), forming the Mn(x)Co(0.056-x)Ga(0.944)N and Cr(x)Ni(0.056-x)Ga(0.944)N quaternary alloys. In order to simulate these systems in a more realistic way, and take into account composition fluctuations, we adapted the generalized quasichemical approach to diluted alloys, which is used in combination with spin density-functional theory. We find that is possible to obtain an AFM ground state up to 70% spin polarization.

1-(2-furoyl)-3-(1-naphthyl)thiourea

In the title compound, C(16)H(12)N(2)O(2)S, the carbonylthiourea group forms dihedral angles of 75.4 (1) and 13.1 (2)degrees, respectively, with the naphthalene ring system and furan ring. The molecule adopts a trans-cis configuration with respect to the positions of the furoyl and naphthyl groups relative to the S atom across the thiourea C-N bonds. This geometry is stabilized by an N-H center dot center dot center dot center dot O intramolecular hydrogen bond. In the crystal structure, molecules are linked by N-H center dot center dot center dot S hydrogen bonds, forming centrosymmetric dimers which are interlinked through C-H center dot center dot center dot pi interactions.

VARIATION IN STOMATAL NUMBERS OF GLOSSOPTERIS LEAVES FROM THE LOWER PERMIAN OF PARANA BASIN, BRAZIL

The stomatal density and index in compressed leaves of Glossopteris communis from two different roof shales from the Lower Permian in Parana Basin, Brazil (Western Gondwana) have been investigated to test the possible relationship with modeled global changes in atmospheric CO(2) during the Phanerozoic. The obtained parameters show that the genus Glossopteris from the Cool Temperate biome can be used as CO(2) -proxy, despite the impossibility of being compared with living relatives or equivalents. When confronted with already published data for the Tropical Summer Wet biome, the present results confirm the detection of low levels of atmospheric CO(2) during the Early Permian, as predicted by the modeled curve. Nevertheless, the lower stomatal numbers detected at the climax of the coal interval (Faxinal Coalfield, Sakmarian) when compared to the higher ones obtained in leaves from a younger interval (Figueira Coalfield, Artinskian) could be attributed to temporarily high levels of atmospheric CO(2). Therefore, the occurrence of an extensive peat generating event at the southern part of the basin and subsequent greenhouse gases emissions from this environment may have been enough to reverse regionally and temporarily the reduction trend in atmospheric CO(2). Additionally, the Faxinal flora is preserved in a tonstein layer, which is a record of volcanic activity that could also cause a rise in atmospheric CO(2). During the Artinskian, the scarce generation of peat mires, as revealed by the occurrence of thin and discontinuous coal layers, and the lack of volcanism evidence would be insufficient to affect the general low CO(2) trend.

DNA damage by sulfite autoxidation catalyzed by cobalt complexes

DNA damage was investigated in the presence of sulfite, dissolved oxygen and cobalt(II) complexes with glycylglycylhistidine, glycylhistidyllysine, glycylglycyltyrosylarginine and tetraglycine. These studies indicated that only Co(II) complexed with glycylglycylhistidine (GGH) induced DNA strand breaks at low sulfite concentrations (1-80 mu M) via strong oxidants formed in the reaction. In the presence of the other complexes, some damage occurred only in the presence of high sulfite concentrations (0.1-2.0 mM) after incubation for 4 h. In the presence of GGH, Co(II) and dissolved O(2), DNA damage must involve a reactive high-valent cobalt complex. The damaging effect was increased by adding S(IV), due to the oxysulfur radicals formed as intermediates in S(IV) autoxidation catalyzed by the complex. SO(3)(center dot)-S-, HO(center dot) and H(center dot) radicals were detected by EPR-spin trapping experiments with DMPO (5,5-dimethyl-1-pyrroline N-oxide). The results indicate that Co(II) binds O2 in the presence of GGH, and leads to the formation of a DMPO-HO(center dot) adduct without first forming free superoxide or hydroxyl radical, supporting the participation of a reactive high-valent cobalt complex.

Singlet molecular oxygen trapping by the fluorescent probe diethyl-3,3 '-(9,10-anthracenediyl)bisacrylate synthesized by the Heck reaction

Singlet molecular oxygen O(2)((1)Delta(g)) is a potent oxidant that can react with different biomolecules, including DNA, lipids and proteins. Many polycyclic aromatic hydrocarbons have been studied as O(2)((1)Delta(g)) chemical traps. Nevertheless, a suitable modification in the polycyclic aromatic ring must be made to increase the yield of O(2)((1)Delta(g)) chemical trapping. With this goal, an anthracene derivative, diethyl-3,3 '-(9,10-anthracenediyl)bisacrylate (DADB), was obtained from the reaction of 9,10-dibromoanthracene and ethyl acrylate through the Heck coupling reaction. The coupling of ethyl acrylate with the anthracene ring produced a new lipophilic, esterified, fluorescent probe reactive toward O(2)((1)Delta(g)). This compound reacts with O(2)((1)Delta(g)) at a rate of k(r) = 1.69 x 10(6) M(-1) s(-1) forming a stable endoperoxide (DADBO(2)), which was characterized by UV-Vis, fluorescence, HPLC/MS and (1)H and (13)C NMR techniques. The photophysical, photochemical and thermostability features of DADB were also evaluated. Furthermore, this compound has the potential for great application in biological systems because it is easily synthetized in large amount and generates specific endoperoxide (DADBO(2)), which can be easily detected by HPLC tandem mass spectrometry (HPLC/MS/MS).

Low-frequency Raman spectra and fragility of imidazolium ionic liquids

Raman spectra within the 5-200 cm(-1) range have been recorded as a function of temperature for different ionic liquids based on imidazolium cations. A correlation has been found between fragility and the temperature dependence of the strength of fast relaxational motions. Understanding quasielastic scattering as the relaxational contribution to ionic mean-squared displacement elucidates some effects on ionic liquids' fragility resulting from modifications in the chemical structure. (C) 2010 American Institute of Physics. [doi:10.1063/1.3462962]

Polarization effects in molecular dynamics simulations of glass-formers Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8

Thermodynamics, equilibrium structure, and dynamics of glass-forming liquids Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8, have been investigated by molecular dynamics (MD) simulations. A polarizable model was considered for H(2)O and NO(3)- on the basis of previous fluctuating charge models for pure water and the molten salt 2Ca(NO(3))(2)center dot 3KNO(3). Similar thermodynamic properties have been obtained with nonpolarizable and polarizable models. The glass transition temperature, T(g), estimated from MD simulations was dependent on polarization, in particular the dependence of T(g) with electrolyte concentration. Significant polarization effects on equilibrium structure were observed in cation-cation, cation-anion, and water-water structures. Polarization increases the diffusion coefficient of H(2)O, but does not change significantly the diffusion coefficients of ions. Viscosity decreases upon inclusion of polarization, but the conductivity calculated with the polarizable model is smaller than the nonpolarizable model because polarization enhances anion-cation interactions.

Fragility and glassy dynamics of 2Ca(NO(3))(2)center dot 3KNO(3) under pressure: Molecular dynamics simulations

Molecular dynamics simulations of the glass-forming liquid 2Ca(NO(3))(2)center dot 3KNO(3) (CKN) were performed from high temperature liquid states down to low temperature glassy states at six different pressures from 10(-4) to 5.0 GPa. The temperature dependence of the structural relaxation time indicates that the fragility of liquid CKN changes with pressure. In line with recent proposal [Scopigno , Science 302, 849 (2003)], the change on liquid fragility is followed by a proportional change of the nonergodicity factor of the corresponding glass at low temperature. (c) 2008 American Institute of Physics.

Intermolecular vibrations and fast relaxations in supercooled ionic liquids

Short-time dynamics of ionic liquids has been investigated by low-frequency Raman spectroscopy (4 < omega < 100 cm(-1)) within the supercooled liquid range. Raman spectra are reported for ionic liquids with the same anion, bis(trifluoromethylsulfonyl)imide, and different cations: 1-butyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-1-methylpiperidinium, trimethylbutylammonium, and tributylmethylammonium. It is shown that low-frequency Raman spectroscopy provides similar results as optical Kerr effect (OKE) spectroscopy, which has been used to study intermolecular vibrations in ionic liquids. The comparison of ionic liquids containing aromatic and non-aromatic cations identifies the characteristic feature in Raman spectra usually assigned to librational motion of the imidazolium ring. The strength of the fast relaxations (quasi-elastic scattering, QES) and the intermolecular vibrational contribution (boson peak) of ionic liquids with non-aromatic cations are significantly lower than imidazolium ionic liquids. A correlation length assigned to the boson peak vibrations was estimated from the frequency of the maximum of the boson peak and experimental data of sound velocity. The correlation length related to the boson peak (similar to 19 angstrom) does not change with the length of the alkyl chain in imidazolium cations, in contrast to the position of the first-sharp diffraction peak observed in neutron and X-ray scattering measurements of ionic liquids. The rate of change of the QES intensity in the supercooled liquid range is compared with data of excess entropy, free volume, and mean-squared displacement recently reported for ionic liquids. The temperature dependence of the QES intensity in ionic liquids illustrates relationships between short-time dynamics and long-time structural relaxation that have been proposed for glass-forming liquids. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3604533]