Studies on Vinyl Polymerization: Polymerization of Methyl Methacrylate by Permanganate-Malonic Acid Initiator System

Aqueous polymerization of methyl methacrylate initiated by the permanganate-malonic acid redox pair has been studied under atmospheric conditions in the temperature range of 35 to 45°C. The effect of monomer, permanganate, and malonic acid concentrations and temperature on the rate of polymerization was studied. The effect of various water-soluble salts and solvents has been investigated. The rate of polymerization of the permanganate-malonic acid system was compared with the rates involved in various other systems consisting of oxalic acid, citric acid, and tartaric acid coupled with permanganate under similar conditions. The end-group of the polymer has been characterized by IR spectra. A suitable kinetic scheme has been proposed, and appropriate rate expressions have been derived on this basis and explained in the light of experimental findings.     

Comparison of electrical conductivity and thermal properties of borosilicate glass with and without simulated radioactive waste

Electrical conductivity and percentage linear thermal expansion of the borosilicate glass (BSG) and simulated waste-loaded borosilicate glass (BSGW) were measured in the temperature range of 300–780 K and compared. Pronounced increase in electrical conductivity was observed around glass transition temperature (T _g) of BSG and BSGW. The activation energy (E _a) of electrical conduction determined from the measured data for BSG and BSGW is 0.961 ± 0.005 and 0.960 ± 0.005 eV, respectively. The % average linear thermal expansion of BSGW showed a slight decreasing trend compared with pristine BSG. The average coefficient of thermal expansion determined from dilatometry data is 12.87 ± 0.24 × 10^?6 and 11.94 ± 0.23 × 10^?6 K^?1 for BSG and BSGW, respectively. The T _g measured by dilatometry is 806 ± 24 K for BSG and 790 ± 23 K for BSGW, respectively. The T _g measured by DTA was found to be 820 ± 7 and 805 ± 5 K for BSG and BSGW, respectively, for heating cycle. The T _g values obtained from DSC measurements are 805 ± 5 and 803 ± 5 K for BSG and BSGW, respectively. The T _g of BSGW showed a slight decrease compared with that of BSG. The values obtained by DSC examination also showed the lowering of T _g values for the waste-loaded composition. The lowering of T _g may be attributed to the interaction of glass-forming agents and simulated waste elements.     

Does Tautomerization of FapyG Influence Its Mutagenicity?

Oxidative degradation of guanine to 2,6‐diamino‐4‐oxo‐5‐formamidopyrimidine (FapyG) is believed to be mutagenic. It has been proposed recently that the enol tautomer of FapyG is mainly responsible for this effect leading to a guanine‐to‐thymine mutation (T. H. Gehrke, U. Lischke, K. L. Gasteiger, S. Schneider, S. Arnold, H. C. Muller, D. S. Stephenson, H. Zipse, T. Carell, Nat. Chem. Biol.­ 2013, 9, 455–461 ). Here, density functional methods suggest that the enol tautomer of FapyG might not be responsible for the proposed guanine‐to‐thymine mutation. Instead, it might result in a guanine‐to‐adenine mutation.     

Organic Superhalogens

Using first‐principles calculations with predictive capability we show that organic molecules having negative electron affinity can be transformed to superhalogens with electron affinities far exceeding that of chlorine, once its core and ligand atoms are suitably replaced. The discovery of organic superhalogens could have significant impact in chemistry, allowing the synthesis of new materials and compounds.     

Synthesis and Characterization of Two Discrete Ln10 Nanoscopic Ladder‐Type Cages: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation

Two unique lanthanide‐based cages [Ln₁₀( L )₅(μ₂‐OH)₆(H₂O)₂₂](Cl)₄?7 H₂O ([Gd₁₀] and [Dy₁₀]) have been synthesized by using a hydrazone‐based ligand H₄ L (H₄ L =2,6‐bis[(3‐methoxysalicylidene)hydrazinecarbonyl]pyridine) and LnCl₃?x H₂O. Structural characterization of [Gd₁₀] reveals an aesthetically pleasing self‐assembly of five L ^4? and ten Gd³⁺ ions forming a 2×[1×5] rectangular array. The ladder‐shaped cage consists of three “rungs” and two “rails” that are occupied by five ligands. Six out of ten gadolinium centers act as rung locks. Further analysis revealed that three chloride ions are encapsulated inside each discrete [Gd₁₀] molecule through hydrogen bonding and other noncovalent interactions. Both the complexes ([Gd₁₀] and [Dy₁₀]) were characterized by powder X‐ray diffraction and thermogravimetric analysis, which shows that they are isostructural in nature. Magnetic investigations reveal that [Gd₁₀] is a good candidate for magnetic refrigeration with a significant entropy change (?ΔS_m) of 37.4 J kg^?1 K^?1 for an applied field of 7 T and at 3 K. Whereas [Dy₁₀] shows single‐molecule‐magnet‐like behavior.     

Confinement of massless particles: Photon

Confinement of massless particles in a suitably chosen dielectric medium is considered. Light waves of selected frequencies are shown to be confined in a medium with dielectric constantε(r)=a/r−b ². A wave theoretical analysis gives equispaced frequency spectrum for the confined light, the radial dependence of its electric wave vector resembling that of hydrogen atom wave functions. In the large frequency limit an eikonal approximation of the problem gives elliptic orbits for the confined rays. Higher frequency orbits are shown to be closer to the centre of the medium than the lower frequency ones.     

Mass spectra of light and heavy mesons in the-Dirac equation with power-law potential

The mass spectra of both light and heavy mesons are studied in the Dirac equation with an equally mixed 4-vector and scalar power-law potential model. This potential provides an excellent fit not only to the mass spectra ofp°, ϕ, Ψ and υ families but also to those ofD, F andB mesons. The light quark masses inp° and ϕ as well as in atom-like mesons are very close to the current quark masses.     

Inelasticity corrections in the elastic proton-deuteron back-angle scattering at intermediate energies

The elastic proton-deuteron scattering cross sections at back angles have been calculated in the light of Kerman-Kisslinger model, using a generalised baryon transfer mechanism on the assumption that theN ^*'s exist (with a probability～1 %) in the deuteron and that the backward peak is caused by their exchange. The effect of numerous competing open inelastic channels at intermediate energies on the elastic cross section is computed in a particularly simple model of Sopkovich. The resultant damping of the back scattering amplitude is expressed directly in terms of the forward angle elastic scattering data. The results are compared with the experimental cross sections in the energy range of 1.5–2.5 GeV.