New low band gap 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c `]bis1,2,5]thiadiazole based conjugated polymers for organic photovoltaics

Two new low band gap D-A structured conjugated polymers, PBDTTBI and PBDTBBT, based on 2-(4-(trifluoromethyl)phenyl)-1H-benzod]imidazole and benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole acceptor units with benzo1,2-b; 3,4-b']dithiophene as a donor unit have been designed and synthesized via a Stille coupling reaction. The incorporation of the benzo1,2-c; 4,5-c']bis1,2,5]thiadiazole unit into PBDTBBT has significantly altered the optical and electrochemical properties of the polymer. The optical band gap estimated from the onset absorption edge is similar to 1.88 eV and similar to 1.1 eV, respectively for PBDTTBI and PBDTBBT. It is observed that PBDTBBT exhibited a deeper HOMO energy level (similar to 4.06 eV) with strong intramolecular charge transfer interactions. Bulk heterojunction solar cells fabricated with a configuration of ITO/PEDOT: PSS/PBDTBBT: PC71BM/Al exhibited a best power conversion efficiency of 0.67%, with a short circuit current density of 4.9 mA cm(-2), an open-circuit voltage of 0.54 V and a fill factor of 25%.

Temperature-Induced Reversible First-Order Single Crystal to Single Crystal Phase Transition in Boc-gamma(4)(R)Val-Val-OH: Interplay of Enthalpy and Entropy

Crystals of Boc-gamma y(4)(R)Val-Val-OH undergo a reversible first-order single crystal to single crystal phase transition at T-c approximate to 205 K from the orthorhombic space group P22(1)2(1) (Z' = 1) to the monoclinic space group P2(1) (Z' = 2) with a hysteresis of similar to 2.1 K. The low-temperature monoclinic form is best described as a nonmerohedral twin with similar to 50% contributions from its two components. The thermal behavior of the dipeptide crystals was characterized by differential scanning calorimetry experiments. Visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light supported the phase transition. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. A detailed comparison of the room-temperature orthorhombic form with the low-temperature (100 K) monoclinic form revealed that the strong hydrogen-bonding motif is retained in both crystal systems, whereas the non-covalent interactions involving side chains of the dipeptide differ significantly, leading to a small change in molecular conformation in the monoclinic form as well as a small reorientation of the molecules along the ac plane. A rigid-body thermal motion analysis (translation, libration, screw; correlation of translation and libration) was performed to study the crystal entropy. The reversible nature of the phase transition is probably the result of an interplay between enthalpy and entropy: the low-temperature monoclinic form is enthalpically favored, whereas the room-temperature orthorhombic form is entropically favored.

Studies of Adsorption Characteristics of Activated Carbons Down to 4.5 K for the Development of Cryosorption Pumps for Fusion Systems

Cryosorption pump is the only possible device to pump helium, hydrogen and its isotopes in fusion environment, such as high magnetic field and high plasma temperatures. Activated carbons are known to be the most suitable adsorbent in the development of cryosorption pumps. For this purpose, the data of adsorption characteristics of activated carbons in the temperature range 4.5 K to 77 K are needed, but are not available in the literature. For obtaining the above data, a commercial micro pore analyzer operating at 77 K has been integrated with a two stage GM cryocooler, which enables the cooling of the sample temperature down to 4.5 K. A heat switch mounted between the second stage cold head and the sample chamber helps to raise the sample chamber temperature to 77 K without affecting the performance of the cryocooler. The detailed description of this system is presented elsewhere. This paper presents the results of experimental studies of adsorption isotherms measured on different types of activated carbons in the form of granules, globules, flake knitted and non-woven types in the temperature range 4.5 K to 10 K using Helium gas as the adsorbate. The above results are analyzed to obtain the pore size distributions and surface areas of the activated carbons. The effect of adhesive used for bonding the activated carbons to the panels is also studied. These results will be useful to arrive at the right choice of activated carbon to be used for the development of cryosorption pumps.

Logarithmic corrections to extremal black hole entropy in N=2, 4 and 8 supergravity

We compute the logarithmic correction to black hole entropy about exponentially suppressed saddle points of the Quantum Entropy Function corresponding to Z(N) orbifolds of the near horizon geometry of the extremal black hole under study. By carefully accounting for zero mode contributions we show that the logarithmic contributions for quarter-BPS black holes in N = 4 supergravity and one-eighth BPS black holes in N = 8 supergravity perfectly match with the prediction from the microstate counting. We also find that the logarithmic contribution for half-BPS black holes in N = 2 supergravity depends non-trivially on the Z(N) orbifold. Our analysis draws heavily on the results we had previously obtained for heat kernel coefficients on Z(N) orbifolds of spheres and hyperboloids in arXiv:1311.6286 and we also propose a generalization of the Plancherel formula to Z(N) orbifolds of hyperboloids to an expression involving the Harish-Chandra character of sl (2, R), a result which is of possible mathematical interest.

Computational Study of the Formation of Short Centrosymmetric N-center dot center dot center dot S Supramolecular Synthon and Related Weak Interactions in Crystalline 1,2,4-Triazoles

A comprehensive analysis of the crystal packing and the energetic features of a series of four biologically active molecules belonging to the family of substituted 4-(benzylideneamino)-3-(4-fluoro-3-phenoxyphenyl)-1H-1,2,4-triazole-5-(4 H)-thione derivatives have been performed based on the molecular conformation and the supramolecular packing. This involves the formation of a short centrosymmetric R-2(2)(8) NH...S supramolecular synthon in the solid state, including the presence of CH...S, CH...O, CH...N, CH...F, CH...Cl, CF...FC, CCl...ClC, and CH...pi intermolecular interactions along with pp stacking to evaluate the role of noncovalent interactions in the crystal. The presence of such synthons has a substantial contribution toward the interaction energy (-18 to -20 kcal/mol) as obtained from the PIXEL calculation, wherein the Coulombic and polarization contribution are more significant than the dispersion contribution. The geometrical characteristics of such synthons favor short distance, and the population of related molecules having these geometries is rare as has been obtained from the Cambridge Structural Database (CSD). Furthermore, their interaction energies have been compared with those present in our molecules in the solid state. The topological characteristics of the NH...S supramolecular synthon, in addition to related weak interactions, CH...N, CH...Cl, CF...FC, and CCl...ClC, have been estimated using the quantum theory of atoms in molecules (QTAIM). In addition, an analysis of the Hirshfeld surface and associated fingerprint plots of these four molecules also have provided a platform for the evaluation of the contribution of different atom...atom contacts, which contribute toward the packing of the molecules in solids.

Frequency and Temperature-Independent Electrical Transport Properties of 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) Glass-Ceramics

The temperature (300-973K) and frequency (100Hz-10MHz) response of the dielectric and impedance characteristics of 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) glasses and glass nanocrystal composites were studied. The dielectric constant of the glass was found to be almost independent of frequency (100Hz-10MHz) and temperature (300-600K). The temperature coefficient of dielectric constant was 8 +/- 3ppm/K in the 300-600K temperature range. The relaxation and conduction phenomena were rationalized using modulus formalism and universal AC conductivity exponential power law, respectively. The observed relaxation behavior was found to be thermally activated. The complex impedance data were fitted using the least square method. Dispersion of Barium Sodium Niobate (BNN) phase at nanoscale in a glass matrix resulted in the formation of space charge around crystal-glass interface, leading to a high value of effective dielectric constant especially for the samples heat-treated at higher temperatures. The fabricated glass nanocrystal composites exhibited P versus E hysteresis loops at room temperature and the remnant polarization (P-r) increased with the increase in crystallite size.

Combinatorial Crystal Synthesis: Structural Landscape of Phloroglucinol:1,2-bis(4-pyridyl)ethylene and Phloroglucinol:Phenazine

A large number of crystal forms, polymorphs and pseudopolymorphs, have been isolated in the phloroglucinol-dipyridylethylene (PGL:DPE) and phloroglucinol-phenazine (PGL:PHE) systems. An understanding of the intermolecular interactions and synthon preferences in these binary systems enables one to design a ternary molecular solid that consists of PGL, PHE, and DPE, and also others where DPE is replaced by other heterocycles. Clean isolation of these ternary cocrystals demonstrates synthon amplification during crystallization. These results point to the lesser likelihood of polymorphism in multicomponent crystals compared to single-component crystals. The appearance of several crystal forms during crystallization of a multicomponent system can be viewed as combinatorial crystal synthesis with synthon selection from a solution library. The resulting polymorphs and pseudopolymorphs that are obtained constitute a crystal structure landscape.

A Reactive Intermediate, Ni-5(C6H4N3)(6)(CO)(4)], in the Formation of Nonameric Clusters of Nickel, Ni-9(C6H4N3)(12)(CO)(6)] and Ni-9(C6H4N3)(12)(CO)(6)].2(C3H7NO)

Three new molecular compounds, Ni-5(bta)(6)(CO)(4)], I, Ni-9(bta)(12)(CO)(6)], II, Ni-9(bta)(12)(CO)(6)]. 2(C3H7NO), III, (bta = benzotriazole) were prepared employing solvothermal reactions. Of these, I have pentanuclear nickel, whereas II and III have nonanuclear nickel species. The structures are formed by the connectivity between the nickel and benzotriazole giving rise to the 5- and 9-membered nickel clusters. The structures are stabilised by extensive pi aEuro broken vertical bar pi and C-H... pi interactions. Compound II and III are solvotamorphs as they have the same 9-membered nickel clusters and have different solvent molecules. To the best of our knowledge, the compounds I-III represent the first examples of the same transition element existing in two distinct coordination environment in this class of compounds. The studies reveal that compound I is reactive and could be an intermediate in the preparation of II and III. Thermal studies indicate that the compounds are stable upto 350(a similar to)C and at higher temperatures (similar to 800(a similar to)C) the compounds decompose into NiO. Magnetic studies reveal that II is anti-ferromagnetic.

Exploring the Crystal Structure Landscape with a Heterosynthon Module: Fluorobenzoic Acid:1,2-Bis(4-pyridyl)ethylene 2:1 Cocrystals

The crystal structure landscape of the 2:1 benzoic acid:dipyridylethylene cocrystal (BA:DPE-I) is explored experimentally with fluoro-substituted benzoic acids and extended with studies employing the Cambridge Structural Database (CSD). The interpretation of the cocrystal landscape is facilitated by considering the kinetically favored and robust acidpyridine heterosynthon as a modular unit. Information based on high-throughput crystallography shows that polymorphs and pseudopolymorphs may belong to the same landscape but arise from different crystallization pathways because of complex and different kinetic features, and secondary synthon preferences. Using the CSD as a guide, the coformer was changed from 1,2-bis(4-pyridyl)ethylene (DPE-I) to 1,2-bis(4-pyridyl)ethane (DPE-II) and this provides an extended interpretation of the BA:DPE-I cocrystal landscape, also highlighting the complexity of the kineticthermodynamic dichotomy during the molecule-to-crystal progression.

Ligand 5,10,15,20-Tetra(N-methyl-4-pyridyl)porphine (TMPyP4) Prefers the Parallel Propeller-Type Human Telomeric G-Quadruplex DNA over Its Other Polymorphs

The binding of ligand 5,10,15,20-tetra(N-methyl-4-pyridyl)porphine (TMPyP4) with telomeric and genomic G-quadruplex DNA has been extensively studied. However, a comparative study of interactions of TMPyP4 with different conformations of human telomeric G-quadruplex DNA, namely, parallel propeller-type (PP), antiparallel basket-type (AB), and mixed hybrid-type (MH) G-quadruplex DNA, has not been done. We considered all the possible binding sites in each of the G-quadruplex DNA structures and docked TMPyP4 to each one of them. The resultant most potent sites for binding were analyzed from the mean binding free energy of the complexes. Molecular dynamics simulations were then carried out, and analysis of the binding free energy of the TMPyP4-G-quadruplex complex showed that the binding of TMPyP4 with parallel propeller-type G-quadruplex DNA is preferred over the other two G-quadruplex DNA conformations. The results obtained from the change in solvent excluded surface area (SESA) and solvent accessible surface area (SASA) also support the more pronounced binding of the ligand with the parallel propeller-type G-quadruplex DNA.

An encaged sigma* orbital in 3-methoxy-2,4,10-trioxaadamantane. Preferred exo-anomeric effect as revealed by the crystal structure

In the titled tricyclic orthocarbonate derivative, the three endocyclic C-O bonds are longer than the exo-cyclic C-O bond (similar to 4.40 angstrom vs. similar to 1.37 angstrom). This indicates an anomeric-type interaction between the two electron lone pairs on the exocyclic oxygen atom and the antibonding orbitals of the two antiperiplanar endocyclic C-O bonds. The remaining endocyclic C-O bond - marginally shorter than the other two apparently adds to this effect. Intriguingly, the antibonding orbital of the exocyclic C-O bond extends into the interior of the adamantyl cage, and is stereoelectronically prevented from overlapping with any of the six adjacent lone pairs. The results also seem to indicate a preference for interaction between a single donor oxygen atom and multiple acceptor antibonding orbitals rather than vice versa. The results add insightfully to the substantial body of evidence favouring the antiperiplanar lone pair hypothesis (ALPH). (C) 2014 Elsevier B.V. All rights reserved.

Rapid reduction of GO by hydrogen spill-over mechanism by in situ generated nanoparticles at room temperature and their catalytic performance towards 4-nitrophenol reduction and ethanol oxidation

Here, we report the clean and facile synthesis of Pt and Pd nanoparticles decorated on reduced graphene oxide (rGO) by the simultaneous reduction of graphene oxide (GO) and the metal ions in Mg/acid medium. As-generated Pt and Pd nanoparticles serve as a heterogeneous catalyst for the further reduction of the rGO by the hydrogen spill-over process. The C/O ratio is much higher as compared to the rGO obtained by the reduction of GO by only Mg/acid. Overall, the process is rapid, facile and green that does not require any toxic chemical agent or any rigorous chemical reactions. We perform the catalytic reduction of 4-nitophenol (4-NP) to 4-aminophenol (4-AP) at room temperature by Pd@rGO and Pt@rGO. The reduction is complete within 35 s for Pd@rGO and 60 s for Pt@rGO when 50 mu g of hybrid catalyst is used for 0.5 ml of 1 mM of 4-NP. In case of ethanol oxidation, the current density for Pd@rGO is comparable to commercial Pt/C but is doubled for Pt@rGO. Overall, both structures show highly stable catalytic activity compared to commercial Pt/C. (C) 2014 Elsevier B.V. All rights reserved.

Uninterrupted galvanic reaction for scalable and rapid synthesis of metallic and bimetallic sponges/dendrites as efficient catalysts for 4-nitrophenol reduction

Here, we demonstrate an uninterrupted galvanic replacement reaction (GRR) for the synthesis of metallic (Ag, Cu and Sn) and bimetallic (Cu M, M=Ag, Au, Pt and Pd) sponges/dendrites by sacrificing the low reduction potential metals (Mg in our case) in acidic medium. The acidic medium prevents the oxide formation on Mg surface and facilitates the uninterrupted reaction. The morphology of dendritic/spongy structures is controlled by the volume of acid used for this reaction. The growth mechanism of the spongy/dendritic microstructures is explained by diffusion-limited aggregate model (DLA), which is also largely affected by the volume of acid. The significance of this method is that the yield can be easily predicted, which is a major challenge for the commercialization of the products. Furthermore, the synthesis is complete in 1-2 minutes at room temperature. We show that the sponges/dendrites efficiently act as catalysts to reduce 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using NaBH4-a widely studied conversion process.

Investigation of dielectric relaxation, Jahn-Teller distortion, and magnetic ordering in Y substituted Pr1-xYxMnO3 (0.1 <= x <= 0.4)

We report structural, magnetic, and dielectric properties of the perovskite compound Pr1-xYxMnO3 (0.1 <= x <= 0.4) studied using dc magnetization, ac susceptibility, neutron powder diffraction, and dielectric techniques. These compounds crystallize in orthorhombic space group (Pnma) in the temperature range 5-300 K. The Mn-O-Mn bond angle decreases with the Y substitution along with an increase in the Jahn-Teller distortion. The Jahn-Teller distortion for Pr0.9Y0.1MnO3 shows an anomalous change near 50 K, below which it falls sharply. Neutron powder diffraction patterns of all reported compositions at low temperature constitute additional magnetic Bragg peaks that suggest magnetic ordering. Magnetic reflections were indexed in the nuclear lattice with the propagation vector k = (0, 0, 0). Rietveld refinement of powder patterns conform to A type antiferromagnetic ordering where moments are aligned ferromagnetically in a-c plane and coupled nearly antiferromagnetically along b-axis resulting in a net ferromagnetic component along the b-direction. The antiferromagnetic transition temperature was deduced from dc magnetization and ac susceptibility data. The transition temperature decreases by nearly 22 K (from 81 K to 59 K) as yttrium content (x) increases from 0.1 to 0.4. Measurements reveal strong frequency dispersion in dielectric constant and dielectric loss. Activation energy and relaxation time are estimated from the Arrhenius plot. It is further shown that relaxation behaviour is altered with yttrium doping concentration. (C) 2015 AIP Publishing LLC.

A gap theorem for Ricci-flat 4-manifolds

Let (M, g) be a compact Ricci-fiat 4-manifold. For p is an element of M let K-max(P) (respectively K-min(p)) denote the maximum (respectively the minimum) of sectional curvatures at p. We prove that if K-max(p) <= -cK(min)(P) for all p is an element of M, for some constant c with 0 <= c < 2+root 6/4 then (M, g) is fiat. We prove a similar result for compact Ricci-flat Kahler surfaces. Let (M, g) be such a surface and for p is an element of M let H-max(p) (respectively H-min(P)) denote the maximum (respectively the minimum) of holomorphic sectional curvatures at p. If H-max(P) <= -cH(min)(P) for all p is an element of M, for some constant c with 0 <= c < 1+root 3/2, then (M, g) is flat. (C) 2015 Elsevier B.V. All rights reserved.