Sulfonation of metallocene‐based polyolefinic elastomers and its influence on physicomechanical properties: Effect of reaction parameters,styrene grafting,and pendant chain length

Direct sulfonation and styrene‐mediated sulfonation were carried out onto metallocene‐based poly(ethylene‐co‐octene) (POE) and poly(ethylene‐co‐butene) (PBE) elastomers to impart polarity on the completely nonpolar rubbery matrices and to prepare a new class of elastomer. The influence of styrene‐grafting and pendant chain length on the degree of sulfonation was also studied. The effects of sulfonation, styrene grafting and styrene‐mediated sulfonation at their optimized levels on various physicomechanical properties were thoroughly investigated, and the resultant properties were correlated with structures of the modified elastomers. Higher extent of sulfonic acid groups were introduced through direct sulfonation in comparison with the styrene‐mediated sulfonation, whereas better thermal and mechanical properties were obtained through styrene‐mediated sulfonation in comparison with the direct sulfonation process. PBE had shown higher degree of sulfonation and percentage grafting than POE. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8023–8040, 2008     

Transition metal catalysed Grignard-like allylic activation across tetragonal tin(II) oxide

The reaction of allyl halide and a carbonyl compound under the aegis of tetragonal tin(II) oxide and catalyticd ⁸,d¹⁰ metal complexes provides the corresponding homoallylic alcohol, via a novel allyl tin intermediate.     

Atomically flat single terminated oxide substrate surfaces

Scientific interest in atomically controlled layer-by-layer fabrication of transition metal oxide thin films and heterostructures has increased intensely in recent decades for basic physics reasons as well as for technological applications. This trend has to do, in part, with the coming post-Moore era, and functional oxide electronics could be regarded as a viable alternative for the current semiconductor electronics. Furthermore, the interface of transition metal oxides is exposing many new emergent phenomena and is increasingly becoming a playground for testing new ideas in condensed matter physics. To achieve high quality epitaxial thin films and heterostructures of transition metal oxides with atomically controlled interfaces, one critical requirement is the use of atomically flat single terminated oxide substrates since the atomic arrangements and the reaction chemistry of the topmost surface layer of substrates determine the growth and consequent properties of the overlying films. Achieving the atomically flat and chemically single terminated surface state of commercially available substrates, however, requires judicious efforts because the surface of as-received substrates is of chemically mixed nature and also often polar. In this review, we summarize the surface treatment procedures to accomplish atomically flat surfaces with single terminating layer for various metal oxide substrates. We particularly focus on the substrates with lattice constant ranging from 4.00 Å to 3.70 Å, as the lattice constant of most perovskite materials falls into this range. For materials outside the range, one can utilize the substrates to induce compressive or tensile strain on the films and explore new states not available in bulk. The substrates covered in this review, which have been chosen with commercial availability and, most importantly, experimental practicality as a criterion, are KTaO₃, REScO₃ (RE = Rare-earth elements), SrTiO₃, La_0.18Sr_0.82Al_0.59Ta_0.41O₃ (LSAT), NdGaO₃, LaAlO₃, SrLaAlO₄, and YAlO₃. Analyzing all the established procedures, we conclude that atomically flat surfaces with selective A- or B-site single termination would be obtained for most commercially available oxide substrates. We further note that this topmost surface layer selectivity would provide an additional degree of freedom in searching for unforeseen emergent phenomena and functional applications in epitaxial oxide thin films and heterostructures with atomically controlled interfaces.     

Montmorillonite K-10 clay catalyzed solvent-free synthesis of bis-indolylindane-1,3-dione, 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-dione and bisindolylindeno[1,2-b]quinoxaline under microwave irradiation

An environmentally benign protocol has been described for the synthesis of novel 2-(1′,3′-dihydro-1H-[2,3′]biindolyl-2′-ylidene)-indan-1,3-diones/bis-indolylindane-1,3-diones from ninhydrin and 3-substituted/unsubstituted indoles. It uses montmorillonite K-10 as catalyst in a solvent-free condition under microwave irradiation. The method was also used for the synthesis of novel bisindolylindeno[1,2-b]quinoxaline derivatives.     

Characterization of solid standards prepared by freeze‐drying

Solid standards prepared by freeze‐drying consistently showed a high degree of homogeneity. The freezing process, completed in fractions of a second, preserves the original homogeneous distribution of the dopants, and the subsequent sublimation step would minimize any disturbance. Compared to those prepared by conventional methods such as blending and spiking, freeze‐dried standards exhibited superior lateral distribution and better uniform depth distribution. There is, however, a concentration constraint for achieving homogeneity. At 5% doping, segregation was observed in both lateral and depth distribution. Many tungsten standards doped with 10–28 elements ranging from 10 to 200 ppm were successfully prepared and used as controls for a number of analytical techniques including glow discharge mass spectrometry (GDMS) and d.c.‐arc optical emission spectroscopy (OES). Copyright © 2009 John Wiley & Sons, Ltd.     

Simultaneous occurrence of energy transfer and photoinduced electron transfer in interactions of hen egg white lysozyme with 4-nitroquinoline-1-oxide

The carcinogenic drug 4-nitroquinoline-1-oxide (4NQO) has been found to bind with the protein hen egg white lysozyme as evident from fluorescence quenching experiments. The binding constant and stoichiometry have been determined. The values of the thermodynamic parameters indicate that the interaction is an enthalpy-driven spontaneous phenomenon. The experimental value of change in free energy is similar to that obtained from the docking study. The far UV circular dichroism spectra show some changes in the secondary structure of protein. The high value of bimolecular quenching constant leads to the possibility of Förster resonance energy transfer (FRET). Along with FRET, the photoinduced electron transfer (PET) from tryptophan residue of protein to 4NQO has also been evident from the transient absorption spectra obtained in laser flash photolysis experiments. The simultaneous occurrence of FRET and PET is the key factor for quenching of intrinsic fluorescence of the protein as it binds with the drug.     

The role of ion-pairing in peak deformations in overloaded reversed-phase chromatography of peptides

The paper reports a study on the role of ion-pairing behind peak deformations, e.g. peak splitting and even peak disappearance, during the elution of a peptide at highly overloaded conditions in reversed-phase chromatography. Deformation of component peaks is not uncommon in chromatography. There are reports which discuss their occurrence, but mostly at analytical scale, while their occurrence is quite common also in the preparative scale, as in the case discussed in this work. This paper first describes the conditions leading to peak splitting and peak disappearance of an industrial peptide, then explains the plausible reasons behind such behaviour, and finally with experimental analysis demonstrates the role of ion-pairing in causing such behaviour.     

Attenuation and modal dispersion models for spatially multiplexed co-propagating helical optical channels in step index fibers

Spatial reuse of optical frequencies has been shown to be possible through a novel spatial domain multiplexing (SDM) technique that uses spatial multiplexer at the input end to launch multiple channels of the same wavelength inside a single strand of carrier fiber and then employs spatial filtering methods to de-multiplex the different optical channels at the output end. The individual SDM channels are confined to dedicated spatial locations inside the fiber while traversing through it owing to helical propagation of light. This presents attenuation and dispersion models of such a system. Experimentally obtained beam profile and resultant crosstalk of two such spatially multiplexed co-propagating SDM channels of the same wavelength over standard step index multimode optical fibers are also presented.     

Quantization dimension for infinite self-similar probabilities

The quantization dimension function for a probability measure induced by a set of infinite contractive similarity mappings and a given probability vector is determined. A relationship between the quantization dimension function and the temperature function of the thermodynamic formalism arising in multifractal analysis is established. The result in this paper is an infinite extension of Graf and Luschgy [S. Graf, H. Luschgy, The quantization dimension of self-similar probabilities, Math. Nachr. 241 (2002) 103-109].