Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins

We describe the synthetically useful enantioselective addition of Br−CX₃ (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)Rh^IIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.     

Gold‐Catalyzed Tandem Cycloisomerization–Halogenation of Chiral Homopropargyl Sulfonamides

Two new gold‐catalyzed tandem cycloisomerization–halogenation reactions of chiral homopropargyl sulfonamides have been developed. Various enantioenriched 3,3‐diiodopyrrolidin‐2‐ols and 3‐fluoropyrrolidin‐2‐ols were obtained in moderate‐to‐good yields with excellent enantio‐ and diastereoselectivity.     

Polymerizable Molecular Silsesquioxane Cage Armored Hybrid Microcapsules with In Situ Shell Functionalization

We prepared core–shell polymer–silsesquioxane hybrid microcapsules from cage‐like methacryloxypropyl silsesquioxanes (CMSQs) and styrene (St). The presence of CMSQ can moderately reduce the interfacial tension between St and water and help to emulsify the monomer prior to polymerization. Dynamic light scattering (DLS) and TEM analysis demonstrated that uniform core–shell latex particles were achieved. The polymer latex particles were subsequently transformed into well‐defined hollow nanospheres by removing the polystyrene (PS) core with 1:1 ethanol/cyclohexane. High‐resolution TEM and nitrogen adsorption–desorption analysis showed that the final nanospheres possessed hollow cavities and had porous shells; the pore size was approximately 2–3 nm. The nanospheres exhibited large surface areas (up to 486 m² g^?1) and preferential adsorption, and they demonstrated the highest reported methylene blue adsorption capacity (95.1 mg g^?1). Moreover, the uniform distribution of the methacryloyl moiety on the hollow nanospheres endowed them with more potential properties. These results could provide a new benchmark for preparing hollow microspheres by a facile one‐step template‐free method for various applications.     

Three-dimensional CFD modeling of transport phenomena in anode-supported planar SOFCs

In this study, a three-dimensional computational fluid dynamics model has been developed for an anode-supported planar SOFC. The conservation equations of mass, momentum, species/charges and thermal energy are solved by finite volume method for a complete unit cell consisting of 13 parallel channels in both anode and cathode. The simulation results of the developed model are well in agreement with the experimental data obtained at same conditions. In this study, the co-flow arrangement with hydrogen utilization of 60 % and operating voltage of 0.7 V is used as the base case, and compared with the counter-flow arrangement. The predicted results reveals that the maximum temperature obtained in the counter-flow arrangement is about 10 °C lower than that of co-flow, but the counter-flow arrangement has a higher temperature gradient between the respective anodes and cathodes in a cross-section normal to the main flow direction, especially in the air inlet region of the cell (x = 0.04 m),which is very harmful to the lifetime of materials. The current density is very unevenly distributed along and normal to the flow direction for both the co- and counter-flow arrangements, and the maximum values occur at junctions of the electrodes, channels and ribs, which causes higher over-potentials and ohmic heating.