Fabrication and characterization of poly(methyl methacrylate)/CaCu3Ti4O12 composites

Composites comprising Poly(Methyl Methacrylate) (PMMA) and CaCu3Ti4O12 (CCTO) via melt mixing followed by hot pressing were fabricated. These were characterized using X-ray diffraction, thermo gravimetric, scanning electron microscopy, and Impedance analyzer for their structural, morphology, and dielectric properties. Composites were found to have better thermal stability than that of pure PMMA. The composite, with 38 Vol % of CCTO (in PMMA), exhibited remarkably low dielectric loss at high frequencies and the low frequency relaxation is attributed to the space charge polarization/MWS effect. Theoretical models were employed to rationalize the dielectric behavior of these composites. At higher temperatures, the relaxation peak shifts to higher frequencies, due to the merging of both beta and alpha relaxations into a single dielectric dispersion peak. The AC conductivity in the high frequency region was attributed to the electronic polarization. POLYM. ENG. SCI., 54:551-558, 2014. (c) 2013 Society of Plastics Engineers

Nanoparticle-Driven Intermolecular Cooperativity and Miscibility in Polystyrene/Poly(vinyl methyl ether) Blends

The effect of silver nanoparticles (nAg) in PS/PVME polystyrene/poly(vinyl methyl ether)] blends was studied with respect to the evolution of morphology, demixing temperature, and segmental dynamics. In the early stage of demixing, PVME developed an interconnected network that coarsened in the late stage. The nAg induced miscibility in the blends as supported by shear rheological measurements. The physicochemical processes that drive phase separation in blends also led to migration of nAg to the PVME phase as supported by AFM. The segmental dynamics was greatly influenced by the presence of nAg due to the specific interaction of nAg with PVME. Slower dynamics and an increase in intermolecular cooperativity in the presence of nAg further supported the role of nAg in delaying the phase separation processes and augmenting the demixing temperature in the blends. Different theoretical models were assessed to gain insight into the dynamic heterogeneity in PS/PVME blends at different length scales.

Reduced graphene oxide induced phase miscibility in polystyrene-poly(vinyl methyl ether) blends

Graphene oxide and reduced graphene oxide (r-GO) were synthesized by wet chemistry and the effect of r-GO in PS-PVME blends was investigated here with respect to phase miscibility, intermolecular cooperativity in the glass transition region and concentration fluctuation variance by shear rheology and dielectric spectroscopy. The spinodal decomposition temperature (T-s) and correlation length were evaluated from isochronal temperature scans in shear rheology. The r-GO is shown to induce miscibility in the blends, which may lead to increased local heterogeneity in the blends, though the length of cooperatively re-arranged regions (xi) at T-g is more or less unaltered. The evolution of the phase morphology as a function of temperature was assessed using polarized optical microscopy (POM). In the case of the 60/40 PS-PVME blends with 0.25 wt% r-GO, apart from significant refinement in the morphology, retention of the interconnected ligaments of PVME was observed, even in the late stages of phase separation suggesting that the coarsening of the phase morphology has been slowed down in the presence of r-GO. This phenomenon was also supported by AFM. Surface enrichment of PVME, owing to its lower surface tension, in the demixed samples was supported by XPS scans. The interconnected network of PVME has resulted in significantly higher permittivity in the bi-phasic blends, although the concentration of r-GO is below the percolation threshold.

Iodide Retention by Modified Kaolinite in the Context of Safe Disposal of High Level Nuclear Waste

Bentonite clay is identified as potential buffer in deep geological repositories (DGR) that store high level radioactive wastes (HLW) as the expansive clay satisfies the expected mechanical and physicochemical functions of the buffer material. In the deep geological disposal of HLW, iodine-129 is one of the significant nuclides, attributable to its long half-life (half life 1⁄4 1:7 × 107 years). However, the negative charge on the basal surface of bentonite particles precludes retention of iodide anions. To render the bentonite effective in retaining hazardous iodide species in DGR, improvement of the anion retention capacity of bentonite becomes imperative. The iodide retention capac-ity of bentonite is improved by admixing 10 and 20% Ag-kaolinite (Ag-K) with bentonite (B) on a dry mass basis. The present study produced Ag-kaolinite by heating silver nitrate-kaolinite mixes at 400°C. Marginal release of iodide retained by Ag-kaolinite occurred under extreme acidic (pH 1⁄4 2:5) and alkaline (pH 1⁄4 12:5) conditions. The swell pressure and iodide etention results of the B-Ag-K specimens bring out that mixing Ag-K with bentonite does not chemically modify the expansive clay; the mixing is physical in nature and Ag-K presence only contributes to iodide retention of the admixture. DOI: 10.1061/(ASCE)HZ.2153-5515.0000121. © 2012 American Society of Civil Engineers.

Iodo( trisyl) sulfane: Reactivity of a Stable Alkanesulfenyl Iodide towards Antithyroid Drugs

Iodination of tris(trimethylsilyl)methanethiol (trisylthiol, TsiSH) in tetrahydrofuran provides the new thermally stable alkanesulfenyl iodide iodo(trisyl)sulfane, TsiSI] as a violet solid. Iodo(trisyl)sulfane exhibits iodine-iodine contacts between pairs of TsiSI molecules in the solid state. Properties of TsiSI were studied by vibrational spectroscopy and with the help of density functional calculations. TsiSI reacts in the presence of triethylamine with the antithyroid drugs 6-n-propyl- and 6-methylthiouracil (PTU, MTU) and with N-methylmethimazole (MMI) to form unsymmetric disulfides that were investigated by means of X-ray crystallography. In the solid state, the PTU and MTU derivatives exist as hydrogen-bonded centrosymmetric dimers, whereas the MMI-derived disulfide is an unsymmetric monomer.

Electromagnetic Interference Shielding Materials Derived from Gelation of Multiwall Carbon Nanotubes in Polystyrene/Poly(methyl methacrylate) Blends

Blends of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with different surface-functionalized multiwall carbon nanotubes (MWNTs) were prepared by solution blending to design materials with tunable EMI (electromagnetic interference) shielding. Different MWNTs like pristine, amine (similar to NH2), and carboxyl acid (similar to COOH) functionalized were incorporated in the polymer by solution blending. The specific interaction driven localization of MWNTs in the blend during annealing was monitored using contact mode AFM (atomic force microscopy) on thin films. Surface composition of the phase separated blends was further evaluated using X-ray photoelectron spectroscopy (XPS). The localization of MWNTs in a given phase in the bulk was further supported by selective dissolution experiments. Solution-casted PS/PMMA (50/50, wt/wt) blend exhibited a cocontinuous morphology on annealing for 30 min, whereas on longer annealing times it coarsened into matrix-droplet type of morphology. Interestingly, both pristine MWNTs and NH2-MWNTs resulted in interconnected structures of PMMA in PS matrix upon annealing, whereas COOH-MWNTs were localized in the PMMA droplets. Room-temperature electrical conductivity and electromagnetic shielding effectiveness (SE) were measured in a broad range of frequency. It was observed that both electrical conductivity and SE were strongly contingent on the type of surface functional groups on the MWNTs. The thermal conductivity of the blends was measured with laser flash technique at different temperatures. Interestingly, the SE for blends with pristine and NH2-MWNTs was >-24 dB at room temperature, which is commercially important, and with very marginal variation in thermal conductivity in the temperature range of 303-343 K. The gelation of MWNTs in the blends resulted in a higher SE than those obtained using the composites.

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.

Performance study of a cesium iodide photocathode-based UV photon detector in Ar/CH4 mixture

The detection efficiency of a gaseous photomultiplier depends on the photocathode quantum efficiency and the extraction efficiency of photoelectrons into the gas. In this paper we have studied the performance of an UV photon detector with P10 gas in which the extraction efficiency can reach values near to those in vacuum operated devices. Simulations have been done to compare the percentage of photoelectrons backscattered in P10 gas as well as in the widely used neon-based gas mixture. The performance study has been carried out using a single stage thick gas electron multiplier (THGEM). The electron pulses and electron spectrum are recorded under various operating conditions. Secondary effects prevailing in UV photon detectors like photon feedback are discussed and its effect on the electron spectrum under different operating conditions is analyzed. (C) 2014 Chinese Laser Press

Synergistic effect of colchicine and iodide ions on the corrosion of mild steel in 0.5 M H2SO4

The inhibition behavior of colchicine (CC) on the corrosion of mild steel in 0.5 M H2SO4 was evaluated by electrochemical methods such as potentiodynamic polarization and electrochemical impedance spectroscopic measurements. The inhibition efficiency increases with increasing concentration of CC. The potentiodynamic polarization results reveal that CC act as a mixed-type inhibitor by retarding both cathodic and anodic corrosion reactions. Additionally, the synergism was carried out between CC and KI to improve the corrosion inhibition behavior of CC on mild steel. The adsorption of both CC alone and the combined inhibitor (CC + KI) on mild steel surface follows Langmuir adsorption isotherm. The synergism parameter (S (theta) ) was calculated to recognize the existence of synergism between CC and iodide ions. Lastly, an adsorption mechanism of CC molecules with iodide ions is discussed.

Self-assembly of Metallamacrocycles Employing a New Benzil-based Organometallic Bisplatinum(II) Acceptor

A benzil-based semi-rigid dinuclear organometallic acceptor 4,4'-bistrans-Pt(PEt3)(2)(NO3)(ethynyl)]benzil (bisPt-NO3) containing a Pt-ethynyl functionality was synthesized in good yield and characterized by multinuclear NMR (H-1, P-31, and C-13), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction analysis of the iodide analogue bisPt-I. The stoichiometric (1:1) combination of the acceptor bisPt-NO3 separately with four different ditopic donors (L-1-L-4; L-1 = 9-ethyl-3,6-di(1H-imidazol-1-yl)-9H-carbazole, L-2 = 1,4-bis((1H-imidazol-1-yl)methyl)benzene, L-3 = 1,3-bis((1H-imidazol-1-yl)methyl)benzene and L-4 = 9,10-bis((1H-imidazol-1-yl) methyl)anthracene) yielded four 2 + 2] self-assembled metallacycles M-1-M-4 in quantitative yields, respectively. All these newly synthesized assemblies were characterized by various spectroscopic techniques (NMR, IR, ESI-MS) and their sizes/shapes were predicted through geometry optimization employing the PM6 semi-empirical method. The benzil moiety was introduced in the backbone of the acceptor bisPt-NO3 due to the interesting structural feature of long carbonyl C-C bond (similar to 1.54 angstrom), which enabled us to probe the role of conformational flexibility on size and shapes of the resulting coordination ensembles.

Evidence for N-7 guanine methyl transferase activity encoded within the modular domain of RNA-dependent RNA polymerase L of a Morbillivirus

Post-transcriptional modification of viral mRNA is essential for the translation of viral proteins by cellular translation machinery. Due to the cytoplasmic replication of Paramyxoviruses, the viral-encoded RNA-dependent RNA polymerase (RdRP) is thought to possess all activities required for mRNA capping and methylation. In the present work, using partially purified recombinant RNA polymerase complex of rinderpest virus expressed in insect cells, we demonstrate the in vitro methylation of capped mRNA. Further, we show that a recombinant C-terminal fragment (1717-2183 aa) of L protein is capable of methylating capped mRNA, suggesting that the various post-transcriptional activities of the L protein are located in independently folding domains.

An Efficient Tertiary Azidation of 1,3-Dicarbonyl Compounds in Water Catalyzed by Tetrabutylammonium Iodide

An efficient azidation of 1,3-dicarbonyl compounds led to tertiary azides in the presence of tetrabutylammonium iodide (TBAI). TBAI is used as a pre-catalyst along with aq. tert-butyl hydroperoxide (TBHP) as an oxidant in aqueous medium. This operationally simple, practical, mild and green method provides an opportunity to synthesize a variety of azidated -keto esters, amides, and ketones in good yields.