Ring Enlargement of Three-Membered Heterocycles by Treatment with In Situ Formed Tricyanomethane

Although the chemistry of elusive tricyanomethane (cyanoform) has been studied during a period of more than 150 years, this compound has very rarely been utilized in the synthesis or modification of heterocycles. Three-membered heterocycles, such as epoxides, thiirane, aziridines, or 2H-azirines, are now treated with tricyanomethane, which is generated in situ by heating azidomethylidene-malonodinitrile in tetrahydrofuran at 45 °C or by adding sulfuric acid to potassium tricyanomethanide. This leads to ring expansion with formation of 2-(dicyanomethylidene)oxazolidine derivatives or creation of the corresponding thiazolidine, imidazolidine, or imidazoline compounds and opens up a new access to these push–pull-substituted olefinic products. The regio- and stereochemistry of the ring-enlargement processes are discussed, and the proposed reaction mechanisms were confirmed by using ¹⁵N-labeled substrates. It turns out that different mechanisms are operating; however, tricyanomethanide is always acting as a nitrogen-centered nucleophile, which is quite unusual if compared to other reactions of this species.     

Formation and Structure of Fluorescent Silver Nanoclusters at Interfacial Binding Sites Facilitating Oligomerization of DNA Hairpins

Fluorescent, DNA‐stabilized silver nanoclusters (DNA‐AgNCs) are applied in a range of applications within nanoscience and nanotechnology. However, their diverse optical properties, mechanism of formation, and aspects of their composition remain unexplored, making the rational design of nanocluster probes challenging. Herein, a synthetic procedure is described for obtaining a high yield of emissive DNA‐AgNCs with a C‐loop hairpin DNA sequence, with subsequent purification by size‐exclusion chromatography (SEC). Through a combination of optical spectroscopy, gel electrophoresis, inductively coupled plasma mass spectrometry (ICP‐MS), and small‐angle X‐ray scattering (SAXS) in conjunction with the systematic study of various DNA sequences, the low‐resolution structure and mechanism of the formation of AgNCs were investigated. Data indicate that fluorescent DNA‐AgNCs self‐assemble by a head‐to‐head binding of two DNA hairpins, bridged by a silver nanocluster, resulting in the modelling of a dimeric structure harboring an Ag₁₂ cluster.     

Intraspecific competition of predator for prey with variable rates in protected areas

Nonlinear Dynamics - In this present study, we systematically explore the periodicity (almost periodic nature) of a dynamical system in time-varying environment, which portrays a special case of...     

Inhibition of LPS-induced no production in RAW264.7 cell lines: synthesis and molecular modeling of α-ketophosphonates of febuxostat

In an effort to develop novel anti-inflammatory agents, we synthesized phosphorylated derivatives of febuxostat using various phosphates/phosphonites by Michaelis-Arbuzov reaction. Their inhibitory activity on nitric oxide (NO) production, reactive oxygen species (ROS) production and cytotoxicity were evaluated using lipopolysaccharide (LPS) activated macrophages RAW264.7 assay, flow-cytometry analysis and MTT method respectively. Some of these compounds showed potent inhibition of NO and ROS production without obvious cytotoxicity. Furthermore, docking simulations were performed to positional compounds 3g, 3h, 3i and 3j into the COX-2 active site to determine the probable binding model. Physicochemical parameters revealed that most of the compounds possessed drug-like properties.     

Nighttime enhancements in TEC near the crest of northern equatorial ionization anomaly during low solar activity period

Enhancement in nighttime total electron content (TEC) near the crest of equatorial ionization anomaly at Bhopal (Geog. 23.2°N, 77.4°E, and MLAT 14.2°N) has been studied for the solar minimum period March 2005- November 2006. TEC data recorded by GPS Ionospheric Scintillation and TEC Monitor (GISTM) GSV4004A receiver is used for the study and results are presented in the paper. More than 10% increase in TEC with respect to background content is considered for analysis. Out of total 138 enhancements, 65 observed during pre midnight hours and 73 during post midnight hours. It is observed that nighttime enhancement in TEC at Bhopal occurs in all seasons; it is more frequent during summer, less during equinox and least during winter months. The enhancement in nighttime TEC can be observed both in geomagnetic disturbed time and in quiet time. We found that mean peak amplitude for pre-midnight TEC enhancement are more in equinox and less in winter, while in post-midnight TEC enhancement it is highest in summer and less in winter. Post-midnight enhancements have smaller peak amplitude as compared to pre-midnight. Also the most probable values for pre- and post-midnights are 4.4 TECU and 2.17 TECU respectively. The percentage occurrence of nighttime TEC enhancement does not show any dependence on solar activity whereas the peak amplitude depends on solar activity. The percentage occurrence of nighttime TEC enhancement decreases as the magnetic activity increases whereas there is no such dependency found with peak amplitude. It is also observed that majority of nighttime TEC enhancements are occurred without scintillation. The localised nighttime TEC enhancements near the crest of equatorial ionization anomaly region have been observed most of the nights during the period of study.     

Misting of non-Newtonian liquids in forward roll coating

Misting of liquids in forward roll coating is a problem under certain conditions. The relaxation time is known to influence misting but the fundamental mechanisms are not clear. A new mechanism for misting of dilute non-Newtonian liquids was proposed based on visualizations with a high-speed camera. With these liquids, filaments were created which sometimes transformed into beads-on-string structures and the beads were ejected as mist droplets when the structures broke. Misting was quantified by measuring sizes of the generated droplets, their count and mass concentration. The measurements were related to elasticity of the solutions through their relaxation times. Small levels of elasticity reduce the amount of misting, but higher levels lead to an increase.     

A ghost fluid Lattice Boltzmann method for complex geometries

A ghost fluid Lattice Boltzmann method (GF‐LBM) is developed in this study to represent complex boundaries in Lattice Boltzmann simulations of fluid flows. Velocity and density values at the ghost points are extrapolated from the fluid interior and domain boundary via obtaining image points along the boundary normal inside the fluid domain. A general bilinear interpolation algorithm is used to obtain values at image points which are then extrapolated to ghost nodes thus satisfying hydrodynamic boundary conditions. The method ensures no‐penetration and no‐slip conditions at the boundaries. Equilibrium distribution functions at the ghost points are computed using the extrapolated values of the hydrodynamic variables, while non‐equilibrium distribution functions are extrapolated from the interior nodes. The method developed is general, and is capable of prescribing Dirichlet as well as Neumann boundary conditions for pressure and velocity. Consistency and second‐order accuracy of the method are established by running three test problems including cylindrical Couette flow, flow between eccentric rotating cylinders and flow over a cylinder in a confined channel. Copyright © 2011 John Wiley & Sons, Ltd.     

Majumdar-Papapetrou class of nonstatic cylindrically symmetric Brans-Dicke-Maxwell fields

We have obtained relations between certain components of the metric and the electromagnetic potentials for source-free Brans-Dicke-Maxwell fields described by a nonstatic cylindrically symmetric Einstein-Rosen metric. These are important, in the sense that they generate a class of solutions that in a way can be said to belong to the class generated by similar relations obtained by Majumdar [1] and Papapetrou [2] for generalized static Einstein-Maxwell fields. The relations have further been used to reduce the B-D Maxwell equations to B-D vacuum equations and vice versa.     

Degradation of inter-atomic bonds during structural phase change in intermediate Ni-clusters (Ni39-Ni49)

Results based on a symmetry- and spin-unrestricted tight-binding molecular-dynamics study are presented for the ground-state geometries of intermediate Ni(n), n in [39,49], clusters. A structural phase change is found to take place around n=43 during which a structural transition from fcc/hcp structure to icosahedral one is observed. This is in good agreement with recent experimental findings. This structural transition is found to be associated with a degradation of the inter-atomic bond energy which indicates that the inter-atomic bond does not only depend on the coordination number of each atom but also on its point group symmetry.     

Magnetic properties of C60 polymers

Magnetic properties of various C60 polymers are calculated using tight-binding molecular-dynamics and ab initio methods. Our results suggest a mechanism involving an interplay between structural defects and sp(3) hybridization to be responsible for the origin of this magnetism. The onset of magnetism is found to occur much more readily for the Rh-C60 polymeric phase with defects than for any of the other polymers, in agreement with the recent experiment. Our estimate of the magnetic moment is also in very good agreement with the value observed in experiment.