Diastereoselective one-pot Wittig olefination-Michael addition and olefin cross metathesis strategy for total synthesis of cytotoxic natural product (+)-varitriol and its higher analogues

A stereoselective route for the total synthesis of anticancer marine natural product (+)-varitriol (1) is detailed herein. The impressive biological activity and interesting structural features of natural (+)-varitriol fuelled us to undertake the synthesis of some higher analogues (1a-j) of this molecule. The key features of the synthetic strategy include one-pot Wittig olefination followed by a highly diastereoselective oxa-Michael addition to assemble stereochemically pure tetrasubstituted THF moiety of the natural varitriol and olefin cross metathesis to couple the aromatic part with tetrasubstituted THF moiety. The total synthesis of title natural product is efficient with 21.8% overall yield for 9 linear steps from D-ribose and thus facilitates the more scaled-up practical route for the synthesis of 1 and its analogues as well. The synthetic (+)-varitriol (1) and its analogues were screened for their cytotoxicity. The present synthetic approach paves the way for preparation of numerous analogues of the title natural product for drug development.     

Thermally stable nonaggregating pyrenylarenes for blue organic light-emitting devices

A new series of thermally stable blue light-emitting nonplanar pyrenylarenes having an amine donor and a nitrile acceptor group was prepared from a ketene-S,S-acetal under conventional heating and/or microwave irradiation. The photophysical, electrochemical, and optical behavior of donor-acceptor pyrenylarenes are demonstrated. The performance of blue light-emitting pyrenylarenes was investigated by fabricating a multilayer device with the device configuration of ITO/PEDOT:PSS (40 nm)/NPB (30 nm)/pyrenylarene (55 nm)/BCP (8 nm)/LiF (0.6 nm)/Al (200 nm), which exhibited low turn-on voltage (5 V) with luminance efficiency of 0.8 Cd/A with nonaggregation behavior in both solution and solid state.     

Effect of diazocine bridgehead modification on the folding of the Wilcox molecular torsion balance: a view from a different angle

Replacing the methano (NCH(2)N) bridgehead with an ethano (NCH(2)CH(2)N) bridgehead affects the conformational equilibrium of the Wilcox molecular torsion balance. With a NCH(2)CH(2)N bridgehead, the phenyl and the cyclohexyl esters prefer the out conformation, whereas with the NCH(2)N bridgehead, they were found to prefer the folded conformation.     

Mapping the x-ray emission region in a laser-plasma accelerator

The x-ray emission in laser-plasma accelerators can be a powerful tool to understand the physics of relativistic laser-plasma interaction. It is shown here that the mapping of betatron x-ray radiation can be obtained from the x-ray beam profile when an aperture mask is positioned just beyond the end of the emission region. The influence of the plasma density on the position and the longitudinal profile of the x-ray emission is investigated and compared to particle-in-cell simulations. The measurement of the x-ray emission position and length provides insight on the dynamics of the interaction, including the electron self-injection region, possible multiple injection, and the role of the electron beam driven wakefield.     

Photocatalytic mineralization study of malachite green on the surface of Mn-doped BiOCl activated by visible light under ambient condition

Manganese doped BiOCl has been synthesized by hydrolysis method and characterized by X-ray diffraction (XRD), scanning electron micrographs (SEM) and diffusive reflectance spectra (DRS) methods. Interesting results have been obtained from diffusive reflectance spectra. XRD results show a decrease in the lattice parameter for Mn-doped BiOCl and UV-vis measurement reveals that there is a shift in the optical absorption edge toward higher wavelength, which indicates a decrease in the band gap upon Mn doping. The increased photocatalytic activity in degradation of malachite green dye by Mn-doped BiOCl might be due to increase in life time of photogenerated electrons and holes due to scavenging of electrons by Mn, charging the particle surface due to electron on the surface, which enhances the adsorption of dye molecules, or/and decreased crystallite size. The effect of key operating parameters have also been investigated. Complete mineralization has been confirmed by COD analysis. An assumptive reaction mechanism has also been proposed.     

Synthesis, structural, optical and electrical properties of metal nanoparticle–rare earth ion dispersed in polymer film

Cu-nanoparticles have been prepared by ablating a copper target submerged in benzene with laser pulses of Nd:YAG (wavelength: 355, 532 nm and 1,064 nm). Colloidal nanoparticles have been characterized by UV–Vis spectroscopy and transmission electron microscopy. The obtained radius for the nanoparticles prepared using 1,064 nm irradiation lies in the range 15–30 nm, with absorption peak at 572 nm. Luminescence properties of Tb³⁺ ions in the presence and absence of Cu-nanoparticles have been investigated using 355 nm excitation. An enhancement in luminescence of Tb³⁺ by local field effect causing increase in lifetime of ⁵D₄ level of Tb³⁺ ion has been observed. Frequency and temperature-dependent conductivity of Tb³⁺ doped PVA thin films with and without Cu-nanoparticles have been measured in the frequency range 20 Hz–1 MHz and in the temperature range 318–338 K (well below its melting temperature). Real part of the conductivity spectra has been explained in terms of power law. The electrical properties of the thin films show a decrease in dc conductivity on incorporation of the Cu-nanoparticles.     

Cyanide-Free Cyanation of sp2 and sp-Carbon Atoms by an Oxazole-Based Masked CN Source Using Flow Microreactors

This work reports a cyanide-free continuous-flow process for cyanation of sp² and sp carbons to synthesize aryl, vinyl and acetylenic nitriles from (5-methyl-2-phenyloxazol-4-yl) boronic acid [OxBA] reagent as a sole source of carbon-bound masked −CN source. Non-toxic and stable OxBA reagent is generated by lithiation-borylation of bromo-oxazole, and the consecutive Suzuki-Miyaura cross-coupling with aryl, vinyl, or acetylenic halides and demasking [4+2]/retro-[4+2] sequence were successfully accomplished to give the desired cyano compounds with reasonably good yields in a four-step flow manner. A unique feature of this cyanation protocol in flow enables to cyanate a variety of sp² and sp carbons to produce a broad spectrum of aryl acetonitrile. It is envisaged that the OxBA based cyanation would replace existing unstable and toxic approaches as well as non-toxic cyanation using two different sources of “C” and “N” to incorporate the −CN group.     

A wavelet-based variational multiscale method for the LES of incompressible flows in a high-order DG-FEM framework

This work focuses upon the development of a wavelet-based variant of the variational multiscale method (VMS) for accurate and efficient large eddy simulation (LES) called wavelet-based VMS-LES (WMS-LES). This approach has been incorporated within the framework of a high-order incompressible flow solver based upon the pressure-stabilized discontinuous Galerkin finite element method (DG-FEM). The VMS approach is designed to produce an a priori scale separation of the governing equations, in a manner which makes no assumptions on either the boundary conditions or the mesh uniformity. Using second-generation wavelets (SGWs) elementwise for scale separation ensures, on one hand, the preservation of the computational compactness of the DG-FEM scheme and, on the other hand, the ability to achieve scale separation in wavenumber space. The optimal space-frequency localization property of the SGW provides an improvement over the commonly used Legendre polynomials. The suitability of the elementwise SGW scale-separation operation as a tool for error indication has been demonstrated in an h-adaptive computation of the reentrant corner test case. Finally, the DG-FEM solver and the WMS-LES method have been assessed through simulations upon the three-dimensional Taylor-Green vortex test case. Our results indicate that the WMS-LES approach exhibits a distinct improvement over the monolevel LES approach. This effect is not produced by a change in the magnitude of the subgrid dissipation but rather by the redistribution of the subgrid dissipation in wavenumber space.     

GeO2/ZnWO4@CNT nanocomposite as a novel anode material for lithium-ion battery

Journal of Solid State Electrochemistry - Single-walled carbon nanotube (SWCNT) wrapped GeO2/ZnWO4 nanocomposite was prepared by single-step solvothermal method. In this work, GeO2/ZnWO4...