Triphilic pentablock copolymers with perfluoroalkyl segment in central position

Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)-b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid–solid phase transition at 63°C before the final crystal melting at 95°C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy.     

The electronic structure of Rhodium: Angle-resolved studies of photoelectron and secondary electron emission

We report electron spectroscopic studies of the Rh(111) surface, with the aim to obtain bulk band-structure information. We have measured normal photoemision using tunable synchrotron radiation in the range of photon energies between 11 eV and 55 eV, and angle-dependent photoemission along the LUX and LKL azimuths using the He resonance lines (=21.2 eV, 40.8 eV). To complement these data, we studied angleresolved secondary electron emission after excitation with electrons and photons. We derive parts of the one-electron energy dispersionE(k) along L, and determine the energies of several bulk critical points (in eV):E(> ₇₊/₈₊)=–2.75±0.10,E(> ₈₊=–0.85±0.10,E(> _7–=16.1±0.5,E(> _6–/> _8–)=20.5±0.5,E(X ₇₊)=–5.0±0.1,E(L ₆₊)=–5.6±0.5,E(L ₆₊/L ₄₊₊₅₊)=–2.65±0.10,E(L ₆₊)=9.0±0.5 eV. Our results are compared to several available band structure calculations.     

Antisymmetry and analytic structure in the spectrum of a uniform Fréchet algebra

Let M be a C-smooth submanifold of a domain GCⁿ. Denote by 0(M) the algebra of germs of holomorphic functions on M, that is, each f0(M) is holomorphic in some neighbourhood of M, the neighbourhood dependent of f. Now define A(M) as the closure of 0(M) with respect to the topology of compact convergence on M.If M coincides with A(M), the spectrum of A(M), we give a necessary and sufficient condition for A(M) such that M is a complex manifold.     

Momentum-resolved bremsstrahlung isochromat spectroscopy of silver surfaces

Angle-resolved bremsstrahlung isochromat spectra of the Ag(100), Ag(110) and Ag(111) surfaces have been measured. Our work extends and complements several earlier investigations of other authors. The data are summarized in the form of final state dispersionsE(k ). Comparison is made to the available theoretical and experimental information. The results for the bulk as well as for the surface-specific features are in excellent to reasonable agreement among each others and with recent calculations.     

A diruthenium-substituted polyoxometalate as an electrocatalyst for oxygen generation

Transition metal heteropolyanions have been used to catalyze a variety of organic oxidations but have not previously been used for O2 generation, despite sharing some structural similarities with dioxoruthenium water-oxidation catalysts. In this study, we report that the di-Ru-substituted polyoxometalate (POM) [Ru2Zn2(H2O)2(ZnW9O34)2]14- can be used to catalyze the electrochemical generation of O2. By comparing the behavior of this compound to that observed using a mono-Ru-substituted POM catalyst, we show that adjacent Ru sites are necessary to observe O2 generation. These observations suggest a reaction pathway involving two Ru-bound oxygen species combining to form O2 and are consistent with the accepted mechanism of electrochemical oxygen evolution. Finally, analysis of the observed electrode kinetics yields a Tafel slope of roughly 120 mV, which is similar to values reported previously for perovskite anodes.