Pressure‐Induced Intersite Bi?M (M=Ru, Ir) Valence Transitions in Hexagonal Perovskites

Pressure‐induced charge transfer from Bi to Ir/Ru is observed in the hexagonal perovskites Ba_3+nBiM_2+nO_9+3n (n=0,1; M=Ir,Ru). These compounds show first‐order, circa 1 % volume contractions at room temperature above 5 GPa, which are due to the large reduction in the effective ionic radius of Bi when the 6s shell is emptied on oxidation, compared to the relatively negligible effect of reduction on the radii of Ir or Ru. They are the first such transitions involving 4d and 5d compounds, and they double the total number of cases known. Ab initio calculations suggest that magnetic interactions through very short (ca. 2.6 Å) M M bonds contribute to the finely balanced nature of their electronic states.     

Direct visualization of layer-by-layer self-assembled multilayers of organometallic polymers

Direct visualization of organometallic-organic and novel all-organometallic multilayer superlattices prepared by layer-by-layer assembly of cationic/anionic polyferrocenylsilane and anionic polystyrene sulfonate polyelectrolytes using a gold coating/transmission electron microscopy (TEM) technique is reported.     

Dominant ion transport processes of ionic liquid electrolyte in poly(3,4-ethylenedioxythiophene)

Electrochemical quartz crystal microgravimetry was used to study movement of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIBTI) into and out of poly(3,4-ethylenedioxythiophene) (PEDOT). In 0.1M EMIBTI/acetonitrile, anionic transport predominates, as is typical of solution-based electrolytes. In pure EMIBTI, on the other hand, the minimal mass change observed during polymer oxidation/reduction was observed to be cation-dominant. PEDOT deposition from dilute EMIBTI solution followed by cycling in neat EMIBTI resulted in rapid decrease of electroactivity. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Harmonic tori in De Sitter spaces S^{2n}_1

We show that all superconformal harmonic immersions from genus one surfaces into de Sitter spaces $S^{2n}_{1}$ with globally defined harmonic sequence are of finite-type and hence result merely from solving a pair of ordinary differential equations. As an application, we prove that all Willmore tori in $S^{3}$ without umbilic points can be constructed in this simple way.     

The preparation and properties of highly conductive nonstoichiometric oxide catalysts

Inter-oxide compounds of rare earth and transition metal oxides can be made highly nonstoichiometric by the partial substitution of divalent ions, such as strontium, for the rare earth element. These compounds become highly conductive when suitably treated in oxygen at high temperatures, and have been found to function as efficient oxidation catalysts at low temperatures between 100–300°C. The thermodynamics, transport properties and catalytic behavior for CO and CH₄ oxidation of some systems having the perovskite or the K₂NiF₄ structure are discussed, e.g. La_1−xSr_xMO_3−δ(M=Cr,Mn,Fe,Co,Y) and La_2−xSr_xCuO_4−δ. The catalytic behavior is similar for the Cr,Mn,Fe and Co perovskites, but the solid electrolyte La_0.8Sr_0.2YO_2.9 has no effect in CO oxidation but the greatest activity for CH₄ oxidation.     

“Bio”‐Macromolecules: Polymer‐Protein Conjugates as Emerging Scaffolds for Therapeutics

Polymer‐protein conjugates are biohybrid macromolecules derived from covalently connecting synthetic polymers with polypeptides. The resulting materials combine the properties of both worlds: chemists can engineer polymers to stabilize proteins, to add functionality, or to enhance activity; whereas biochemists can exploit the specificity and complexity that Nature has bestowed upon its macromolecules. This has led to a wealth of applications, particularly within the realm of biomedicine. Polymer‐protein conjugation has expanded to include scaffolds for drug delivery, tissue engineering, and microbial inhibitors. This feature article reflects upon recent developments in the field and discusses the applications of these hybrids from a biomaterials standpoint.

     

Fractal analysis of size effects and surface morphology effects in catalysis and electrocatalysis

Fractal geometry tools are used in order to analyze several related problems in surface science, catalysis, and electrocatalysis. The effects of complex morphologies of adsorbents, catalysts, and electrodes on various molecular processes with these materials are determined both theoretically and experimentally. It is shown that fractal geometry provides a convenient and natural tool for the elucidation of geometry-performance relations in heterogeneous chemistry. Issues covered are particle size effects in physisorption and chemisorption; morphology effects on a variety of catalytic processes with unsupported catalysts (including coal liquefaction, alkene polymerizations, oxidations, dehydrogenations, and esterifications); surface accessibility effects on molecular interactions in an Eley-Rideal mechanism; surface patterning effects on concentration profiles near the surface; and electrode-morphology effects on a variety of electrochemical and electrocatalytic processes. The domains of applicability of the fractal approach to these problems is discussed.     

The Kawasaki identity and the Fluctuation Theorem

In this paper we show that the Fluctuation Theorem of Evans and Searles [D. J. Evans, D. J. Searles, Phys. Rev. E 50, 1645 (1994)] implies that the Kawasaki function exp(-Omega(t)) is unity for all time t. We confirm this relationship using experimental data obtained using optical tweezers, and show that the Kawasaki function is a valuable diagnostic tool.     

Minimal Lagrangian 2-Tori in CP2 Come in Real Families of Every Dimension

It is shown that for every non-negative integer n, there isa real n-dimensional family of minimal Lagrangian tori in CP²,and hence of special Lagrangian cones in C³ whose link is atorus. The proof utilises the fact that such tori arise fromintegrable systems, and can be described using algebro-geometric(spectral curve) data.