Reaction of 2-(arylazo)pyridine complexes of type [OsX2L2] (X = Cl or Br) with heterocyclic bases (B): spectra and electrochemistry of [OsX(B)L2]ClO4·H2O

Summary The synthesis and characterization of a series of complexes of the type [OsX(B)L₂] ⁺ (X = Cl or Br, B = pyridine (py) and pyrazine (pyz), L = 2-(phenylazo)pyridine (L¹) or 2-(m-tolylazo)pyridine (L²)) is described. The cations have been isolated as crystalline perchlorate monohydrates after purification by column chromatography. The diamagnetic compounds display several spin-allowed and spin-forbidden m.l.c.t. transitions in the visible region. The metal-centred oxidations and ligand-based reductions of the complexes are studied electrochemically in MeCN. Two consecutive one-electron oxidations corresponding to Os^III/Os^II and Os^IV/Os^III couples occur at ca. 1.3 and ca. 2.3 V versus s.c.e. respectively. Four successive azo-reductions are observable in the potential range -0.4 to -2.4V.     

Effect of Nanoclay on the Morphology and Properties of Nylon 6 and Poly(Methyl Methacrylate) (PMMA) Blends

The effect of organomodified nanoclay on the morphology and properties of a (70/30 w/w) nylon 6/poly(methyl methacrylate) (PMMA) blend prepared by a melt processing method was investigated. The number average domain diameter (D_n ) of the dispersed PMMA phase was found to decrease with the addition of a small amount [0.5 per hundred resin (phr)] of clay in the blend. A much finer dispersion of the minor phase in the presence of a higher amount (5 phr) of clay indicated better mixing efficiency and improved morphology in the blend. X-ray diffraction indicated the exfoliation of the clays in the nylon 6 matrix, whereas PMMA chains only intercalated into the clay layers. However, the same effect of the clay was not observed in a (30/70 w/w) nylon 6/PMMA blend when nylon 6 became the dispersed domains. In the (30/70 w/w) nylon 6/PMMA blend, the addition of organomodified nanoclay (up to 2 phr) increased the D_n of the nylon 6 domains by preferential location of the clays inside the nylon 6 domains. Addition of styrene-maleic anhydride (SMA) copolymer effectively reduced the D_n of disperse phases in both compositions of the nylon 6/PMMA blends. Thus, in nylon 6/PMMA blends, clay platelets could prevent the coalescence of dispersed domains during melt mixing as long as it was dispersed in the matrix phase of the blend. Mechanical properties and thermal stability of the blends were also improved in the presence of clay.     

Emergence of Paramagnetism in Organic Macromolecules during Synthesis

Paramagnetism in polyaniline can be generated during synthesis if cerium (IV) ammonium nitrate (CAN) is used as a polymerizing (oxidizing) agent. During the reaction, in situ formation of Ce³⁺ ions are doped in the spherical polyaniline particles and show paramagnetic behavior throughout the experimental temperature range (400–1.9 K). The result indicated that the Ce³⁺ ions covalently functionalized with the chain nitrogen of the polyaniline.     

A Rapid Method for the Determination of Trace Element Impurities in Silicons Oils by ICP-MS After Microwave-Assisted Digestion

Abstract

A microwave-assisted digestion procedure has been developed for the treatment of silicone oil samples. Inductively coupled plasma mass spectrometry (ICP-MS) was used to determine the concentration level of 40 trace element impurities, like Li, Na, Mg, Al, P, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Sr, Rb, Zr, Nb, Mo, Ag, Cd, Sn, Sb, Ba, La, Ce, Nd, Hf, W, Au, Pb, Hg, Th, Bi and U in these samples, having obtained average relative standard deviation values of 9.6%. The methodology developed has been tested by recovery studies on different natural samples spiked with known amounts of Mg, Cr, Mn, Fe, Zn and Pb at concentration levels of 10, 0.5, 5, 5, 10 and 1 μg g^?1 and recovery percentage values varies from 97 to 105 %.     

Efficient Entrapment of Dye in Hollow Silica Nanoparticles: Direct Evidence Using Fluorescence Spectroscopy

Using hollow silica nanoparticles we demonstrate a simple and highly efficient way of removing hydrophilic dye (Rhodamine B) from water by encapsulation within these hollow spheres. The hollow silica spheres were obtained by using a surfactant templated procedure. Using fluorescence spectroscopy, we also show the evidence of the dye being absorbed within the hollow core of the silica shell (which is crucial for many applications) and differentiate from the adsorption of dye on the surface of the silica shell. It was found that that up to 94 % of the hydrophilic dye could be entrapped using these hollow shells within 72 h of exposure. Fluorescence spectroscopy shows a red shift in the dye encapsulated in the hollow silica which is due to aggregation of the dye and enables us to follow quantitatively the uptake of the dye molecules by the silica shells with time. The evidence for the encapsulation of the dye in these hollow spheres was reinforced by carrying out a comparative study, using solid silica particles.

An investigation into flow mode transition and pressure fluctuations for fluidized dense-phase pneumatic conveying of fine powders

This paper presents the results of an ongoing investigation into the fluctuations of pressure signals due to solids-gas flows for dense-phase pneumatic conveying of fine powders.Pressure signals were obtained from pressure transducers installed along different locations of a pipeline for the fluidized dense-phase pneumatic conveying of fly ash(median particle diameter 30μm;particle density 2300kg/m~3;loosepoured bulk density 700kg/m~3) and white powder(median particle diameter 55 u.m;particle density1600kg/m~3;loose-poured bulk density 620kg/m~3) from dilute to fluidized dense-phase.Standard deviation and Shannon entropy were employed to investigate the pressure signal fluctuations.It was found that there is an increase in the values of Shannon entropy and standard deviation for both of the products along the flow direction through the straight pipe sections.However,both the Shannon entropy and standard deviation values tend to decrease after the flow through bend(s).This result could be attributed to the deceleration of particles while flowing through the bends,resulting in dampened particle fluctuation and turbulence.Lower values of Shannon entropy in the early parts of the pipeline could be due to the non-suspension nature of flow(dense-phase),i.e.,there is a higher probability that the particles are concentrated toward the bottom of pipe,compared with dilute-phase or suspension flow(high velocity),where the particles could be expected to be distributed homogenously throughout the pipe bore(as the flow is in suspension).Changes in straight-pipe pneumatic conveying characteristics along the flow direction also indicate a change in the flow regime along the flow.     

Holographic Image Denoising using Random Laser Illumination

In holographic applications, coherent lasers are indispensable source of illumination. Despite high intensity from coherent light sources, they fail in full-field image projection and illustrate speckle images due to high spatial coherence. This article demonstrates speckle-free high contrast computer-generated holographic image projection upon illumination with a perovskite–polystyrene 10 wt%-based random laser. Solvent-engineered efficient and durable perovskite and perovskite–polystyrene 10 wt%-based random lasers are fabricated. Optical characterizations are elucidated and controlled coherence random lasing operation is achieved under room temperature upon addition of polystyrene concentration 10 wt% on perovskite thin film. The addition of 10 wt% polystyrene concentration results in a low far-field divergence angle of ≈10⁰. The controlled coherence in random lasers is necessary to produce a stable interference pattern and to retain the depth of field in holograms. Additionally, the holographic image projection using random lasers reduces diffraction noise, and exhibits high spatial resolution with full-field imaging. Moreover, this study is clear evidence of an effective strategy to achieve high-performance, indigenous designed-controlled coherence in disordered random lasing media and its application to novel holographic image projection.     

Conversion of nuclear to 2-flavour quark matter in rotating compact stars: A general relativistic perspective

The conversion of neutron star to strange star is argued to be a two step process. The first process involves the deconfinement of nuclear to two-flavour quark matter. The GR results shows that the propagating front breaks up into fragments which propagate with different velocities along different directions. The time taken for this conversion to happen is of the order of few ms. This calculation indicates the inadequacy of non-relativistic (NR) or even Special Relativistic (SR) treatments for these cases.     

Isolation of a Diylide‐Stabilized Stannylene and Germylene: Enhanced Donor Strength through Coplanar Lone Pair Alignment

The preparation of the first stable diylide‐substituted stannylene and germylene ( Y₂E, with E=Ge, Sn and Y=[PPh₃‐C‐SO₂Tol]^?) is reported. The synthesis is easily accomplished in one step from the sulfonyl‐substituted metalated ylide YNa and the corresponding ECl₂ precursors. Y₂Ge and Y₂Sn exhibit unusual structures in the solid state and in solution, in which the three adjacent lone pairs in the C‐E‐C linkage are arranged coplanar to each other. As shown by DFT studies, this bonding situation is preferred over the typical π‐donation from the ligands into the empty p‐orbital at the metal due to the strong anion‐stabilizing ability of the sulfonyl groups in the ylide backbone and their additional coordination to the metal. The alignment of the three lone pairs leads to a remarkable boost of the HOMO energy and thus of the donor strengths of the tetrylenes. Hence, Y₂Ge and Y₂Sn become stronger donors than their diamino or diaryl congeners and comparable to cyclic alkyl(amino)carbenes. First reactivity studies confirm the high reactivity of Y₂Ge and Y₂Sn , which for example undergo an intramolecular C?H activation reaction via metal–ligand cooperation.     

Ultrafast Raman loss spectroscopy

This paper deals with a new form of nonlinear Raman spectroscopy called ‘ultrafast Raman loss spectroscopy (URLS)’. URLS is analogous to stimulated Raman spectroscopy (SRS) but is much more sensitive than SRS. The signals are background (noise) free unlike in coherent anti‐Stokes Raman spectroscopy (CARS) and it provides natural fluorescence rejection, which is a major problem in Raman spectroscopy. In addition, being a self‐phase matching process, the URLS experiment is much easier than CARS, which requires specific phase matching of the laser pulses. URLS is expected to be alternative if not competitive to CARS microscopy, which has become a popular technique in applications to materials, biology and medicine. Copyright © 2009 John Wiley & Sons, Ltd.