Spontaneous Cu(I)Br–PMDETA‐mediated polymerization of isobornyl methacrylate in heterogeneous aqueous medium at ambient temperature

Isobornyl methacrylate (IBMA), a bulky hydrophobic methacrylate, undergoes very fast polymerization, in bulk, with Cu(I)Br/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA)/ethyl‐2‐bromoisobutyrate system, at ambient temperature. IBMA also undergoes a spontaneous initiator‐free polymerization, at ambient temperature, with Cu(I)Br/PMDETA catalytic system in dimethyl sulfoxide–water mixtures. The rate of the polymerization is seen to increase with the water content up to 80 mol % of water. A possible intervention of air in initiation is proposed. The active Cu(0) formed by the disproportionation of Cu(I) species in aqueous medium probably plays a vital role for a possible air‐initiation of IBMA via single electron transfer‐living radical polymerization (SET‐LRP) mechanism. A high tolerance level to water under SET‐LRP conditions is demonstrated. The poly(IBMA) samples obtained exhibit low molecular weight distributions (1.1–1.3). Similar behavior was not observed with other common methacrylates such as methyl methacrylate, t‐butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Single electron transfer‐living radical polymerization of methyl methacrylate catalyzed by ytterbium powder

Zerovalent ytterbium (Yb) powder is firstly used as a catalyst in single electron transfer‐living radical polymerization of methyl methacrylate initiated by carbon tetrachloride in N, N‐dimethylformamide (DMF) and dimethyl sulfoxide, respectively. Polymerization proceeds in a “living”/controlled way as evidenced by kinetic studies and chain extension results, producing well‐defined polymers with controlled degree of polymerization and narrow molecular weight distribution. The apparent activation energy of polymerization in DMF is accounted to be 36.2 kJ/mol, and the energy of equilibrium state is calculated to be 13.9 kJ/mol. An increase in the concentration of Yb(0) yields a higher monomer conversion. It is observed that polymerization rate experiments a rapid increase in the presence of more polar solvent water, and increasing in the content of H₂O results in an increase in the apparent rate constant of polymerization, and a decrease in the molecular weight distribution. The reaction rate and molecular weight increase along with the decrease of DMF content. The effect of Yb(0) powder content, different ligands and concentration of initiator on the polymerization is also investigated. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

A Theory of Electron Transfer in Bridged and Supramolecular Systems

Expressions are derived for the tunnel electric current between two metals produced by the adiabatic transitions of the electrons through a bridge electron level. A new possible physical phenomenon is discussed, viz. electronically driven oscillations of the electron bridge level between two molecular wires.     

Spin-orbit-like terms in semileptonic weak Hamiltonian

It is shown that new spin-orbit-like terms appear in the effective nonrelativistic weak Hamiltonian for nucleon provided that nuclear potential is taken into account. Arguments for their considerable enhancement, in particular, in relativistic nuclear model of Walecka are advanced. Received: 29 July 1999     

Dynamic nuclear polarization studies of nitroxyl spin probes in agarose gel using Overhauser‐enhanced magnetic resonance imaging

Agarose is a tissue‐equivalent material and its imaging characteristics similar to those of real tissues. Hence, the dynamic nuclear polarization studies of 3‐carboxy‐2,2,5,5‐tetramethyl‐pyrrolidine‐1‐oxyl (carboxy‐PROXYL) in agarose gel were carried out. The dynamic nuclear polarization parameters such as spin lattice relaxation time, longitudinal relaxivity, leakage factor, saturation parameter and coupling parameter were estimated for 2 mM carboxy‐PROXYL in phosphate‐buffered saline solution and water/agarose mixture (99 : 1). From these results, the spin probe concentration was optimized as 2 mM, and the reduction in enhancement was observed for carboxy‐PROXYL in water/agarose mixture (99 : 1) compared with phosphate‐buffered saline solution. Phantom imaging was also performed with 2 mM concentration of carboxy‐PROXYL in various concentrations of agarose gel at various radio frequency power levels. The results from the dynamic nuclear polarization measurements agree well with the phantom imaging results. These results pave the way for designing model system for human tissues suited to the biological applications of electron spin resonance/Overhauser‐enhanced magnetic resonance imaging.     

Role of Ag addition in L10 ordering of FePt-based nanocomposite magnets

The FePt system has important perspectives as high-temperature corrosion-resistant magnets. In the form of rapidly solidified melt-spun ribbons, FePt-based magnets may exhibit in certain cases a two-phase hard–soft magnetic behaviour. The present paper deals with a microstructural and magnetic study of FePtAgB alloys with increasing Ag content. The aim is to identify and confirm the effect of Ag addition in decreasing the temperature of the FePt disorder–order structural phase transformation. A detailed high-resolution transmission electron microscopy study is employed, and the alternative disposal of hard and soft regions within the two-phase microstructure is observed and interpreted with respect to the X-ray diffraction results. In the as-cast Ag-containing samples, it is shown that there is an optimum of the Ag content for which best magnetic properties are obtained. Ag addition creates a nonlinear behaviour of the coercive field and the ordering parameter, similar to the RKKY interaction-induced interlayer exchange coupling (IEC) observed in magnetic layers separated by non-magnetic spacer layers. Direct formation of the L1₀ phase from the as-cast state in the FePtAgB alloys is reported with magnetic parameters compatible to other exchange spring permanent nanomagnets. These findings open novel perspectives into utilization of such alloys in applications requiring magnets operating in high-temperature industrial environments.     

Conduction of Strongly Coupled Electrons Through Narrow Channels on Liquid Helium Surface: Simulation

The conduction of electrons through narrow channels formed on the surface of liquid helium is analyzed by numerical simulations. It is shown that, when electrons are strongly coupled, we have nonlinear and even negative dependence of conductance on the width of the constriction which is controlled by the gate voltage (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)