Catalytic Borylation using an Air‐Stable Zinc Boryl Reagent: Systematic Access to Elusive Acylboranes

The use of borylzinc reagents in palladium‐catalyzed borylation chemistry is described (i.e. a boron analogue of the Negishi coupling), including a one‐pot bench‐top protocol using an air‐ and moisture‐stable bis(boryl)zinc reagent. The steric/electronic properties of the boryl fragment employed enable a systematic method for accessing acylboranes, a rare class of organoboron species with great potential in chemical synthesis. The reactions proceed under mild conditions, use inexpensive commercial sources of palladium, and demonstrate a remarkable functional‐group tolerance.     

Lithium‐Salt‐Containing High‐Molecular‐Weight Polystyrene‐block‐Polyethylene Oxide Block Copolymer Films

Ionic conductivity in relation to the morphology of lithium‐doped high‐molecular‐weight polystyrene‐block‐polyethylene oxide (PS‐b‐PEO) diblock copolymer films was investigated as solid‐state membranes for lithium‐ion batteries. The tendency of the polyethylene (PEO) block to crystallize was highly suppressed by increasing both the salt‐doping level and the temperature. The PEO crystallites completely vanished at a salt‐doping ratio of Li/EO>0.08, at which the PEO segments were hindered from entering the crystalline unit of the PEO chain. A kinetically trapped lamella morphology of PS‐b‐PEO was observed, due to PEO crystallization. The increase in the lamella spacing with increasing salt concentration was attributed to the conformation of the PEO chain rather than the volume contribution of the salt or the previously reported increase in the effective interaction parameter. Upon loading the salt, the PEO chains changed from a compact/highly folded conformation to an amorphous/expanded‐like conformation. The ionic conductivity was enhanced by amorphization of PEO and thereby the mobility of the PEO blocks increased upon increasing the salt‐doping level.     

Uniform Reduction of Scalar Coupling by Real‐Time Homonuclear J‐Downscaled NMR

Scalar coupling in proton NMR spectra provides important information for the structural analysis. However, the low resolution due to the resulting signal splitting, together with the rather narrow spectral range of hydrogen, often prevents the extraction of J‐coupling information. Here we present a method to achieve real‐time homonuclear J‐downscaling. Thereby, all J‐values are uniformly reduced by an arbitrary scaling factor. In the resulting one‐dimensional spectra, signal overlap is reduced, while scalar coupling information is still available.     

Gluing Eguchi‐Hanson Metrics and a Question of Page

In 1978, Gibbons‐Pope and Page proposed a physical picture for the Ricci flat Kähler metrics on the K3 surface based on a gluing construction. In this construction, one starts from a flat torus with 16 orbifold points and resolves the orbifold singularities by gluing in 16 small Eguchi‐Hanson manifolds that all have the same orientation. This construction was carried out rigorously by Topiwala, LeBrun‐Singer, and Donaldson. In 1981, Page asked whether the above construction can be modified by reversing the orientations of some of the Eguchi‐Hanson manifolds. This is a subtle question: if successful, this construction would produce Einstein metrics that are neither Kähler nor self‐dual. In this paper, we focus on a configuration of maximal symmetry involving eight small Eguchi‐Hanson manifolds of each orientation that are arranged according to a chessboard pattern. By analyzing the interactions between Eguchi‐Hanson manifolds with opposite orientation, we identify a nonvanishing obstruction to the gluing problem, thereby destroying any hope of producing a metric of zero Ricci curvature in this way. Using this obstruction, we are able to understand the dynamics of such metrics under Ricci flow as long as the Eguchi‐Hanson manifolds remain small. In particular, for the configuration described above, we obtain an ancient solution to the Ricci flow with the property that the maximum of the Riemann curvature tensor blows up at a rate of , while the maximum of the Ricci curvature converges to 0.© 2016 Wiley Periodicals, Inc.     

Effector Regulated Catalytic Cyclization of Alkynoic Acids Using Pt2L4 Cages

Metabolic pathways are highly regulated by effector molecules that influences the rate of enzymatic reactions. Inspired by the catalytic regulation found in living cells, we report a Pt₂L₄ cage of which the activity can be controlled by effectors that bind inside the cage. The cage shows catalytic activity in the lactonization of alkynoic acids, with the reaction rates dependent on the effector guest bound in the cage. Some effector guests enhance the rate of the lactonization by up to 19-fold, whereas one decreases it by 5-fold. When mixtures of specific substrates are used, both starting materials and products act as guests for the Pt₂L₄ cage, enhancing its catalytic activity for one substrate while reducing its activity for the other. The reported regulatory behavior obtained by the addition of effector molecules paves the way to the development of more complex, metabolic-like catalyst systems.