Enantioselective Organocatalytic Singly Occupied Molecular Orbital Activation: The Enantioselective α-Enolation of Aldehydes

The first enantioselective organocatalytic α-enolation of aldehydes has been accomplished using singly occupied molecular orbital (SOMO) catalysis. Chiral secondary amines react with aldehydes to form transient enamines that undergo selective one-electron oxidation to generate electrophilic radical cations. These SOMO-activated radical cations are susceptible to attack by ketone-derived enol silanes, rendering α-substituted-γ-ketoaldehyde products with uniformly high levels of asymmetric induction. Wide latitude in both the aldehyde and enolsilane component is readily accommodated, allowing generic access to a diverse assortment of enantioenriched 1,4-dicarbonyl compounds. This report highlights the potential of SOMO catalysis to enable the development of entirely new classes of asymmetric reactions that have no traditional catalytic equivalents

Hysteresis and the dynamic phase transition in thin ferromagnetic films

Hysteresis and the non-equilibrium dynamic phase transition in thin magnetic films subject to an oscillatory external field have been studied by Monte Carlo simulation. The model under investigation is a classical Heisenberg spin system with a bilinear exchange anisotropy in a planar thin film geometry with competing surface fields. The film exhibits a non-equilibrium phase transition between dynamically ordered and dynamically disordered phases characterized by a critical temperature Tcd, whose location of is determined by the amplitude H0 and frequency w of the applied oscillatory field. In the presence of competing surface fields the critical temperature of the ferromagnetic-paramagnetic transition for the film is suppressed from the bulk system value, Tc, to the interface localization-delocalization temperature Tci. The simulations show that in general Tcd < Tci for the model film. The profile of the time-dependent layer magnetization across the film shows that the dynamically ordered and dynamically disordered phases coexist within the film for T < Tcd. In the presence of competing surface fields, the dynamically ordered phase is localized at one surface of the film.Comment: PDF file, 21 pages including 8 figure pages; added references,typos added; to be published in PR

Electronic modulation of infrared emissivity in graphene plasmonic resonators

Electronic control of blackbody emission from graphene plasmonic resonators on a silicon nitride substrate is demonstrated at temperatures up to 250 C. It is shown that the graphene resonators produce antenna-coupled blackbody radiation, manifest as narrow spectral emission peaks in the mid-IR. By continuously varying the nanoresonators carrier density, the frequency and intensity of these spectral features can be modulated via an electrostatic gate. We describe these phenomena as plasmonically enhanced radiative emission originating both from loss channels associated with plasmon decay in the graphene sheet and from vibrational modes in the SiNx.Comment: 17 pages, 6 figure

Discovery From Non-Parties (Third-Party Discovery) in International Arbitration

International arbitration rules and many arbitration laws usually provide procedures that permit tribunals to order parties to disclose documents and other materials to the other parties.1 More complex are the rules that determine opportunities to obtain discovery from persons that are not party to the arbitration (third-party discovery). This article will review third-party discovery under the Federal Arbitration Act (FAA) and the provisions of the US Code s.1782 that authorise US courts to act in aid of actions before foreign tribunals. Section 1782 has unique interest at this time because it figured prominently in the EU antitrust investigation of Intel that was initiated on request from Advanced Micro Devices (AMD). Early in that investigation, AMD filed a s.1782 request in the US District Court to obtain evidence from US sources for submission to the DG-Competition of the European Commission (EC). This request ultimately led to the Supreme Court’s decision in Intel Corp v Advanced Micro Devices Inc2 which appeared to significantly expand the scope of s.1782. Ironically, after AMD won on key legal issues in the Supreme Court, the District Court on remand exercised its discretion and denied the request for judicial assistance. This paper first describes the FAA non-party discovery rules and the split among the federal appellate courts concerning the authority of arbitrators to order prehearing discovery from non-parties. Next, it provides an analysis of the meaning of the terms “interested party” and “tribunal”—terms that were controversially interpreted by the Supreme Court in Intel and are essential to the application of s.1782. Finally, it discusses the “discretionary” factors used by the federal courts in deciding whether to grant a s.1782 request even when the statutory criteria are met. The opportunity to exercise this discretion seems to rebut the argument that the Supreme Court’s interpretation of s.1782 gives participants before foreign tribunals more discovery rights in the United States than are available to the parties in arbitrations covered by the FAA

Tailoring a two-dimensional electron gas at the LaAlO3/SrTiO3 (001) interface by epitaxial strain

Recently a metallic state was discovered at the interface between insulating oxides, most notably LaAlO3 and SrTiO3. Properties of this two-dimensional electron gas (2DEG) have attracted significant interest due to its potential applications in nanoelectronics. Control over this carrier density and mobility of the 2DEG is essential for applications of these novel systems, and may be achieved by epitaxial strain. However, despite the rich nature of strain effects on oxide materials properties, such as ferroelectricity, magnetism, and superconductivity, the relationship between the strain and electrical properties of the 2DEG at the LaAlO3/SrTiO3 heterointerface remains largely unexplored. Here, we use different lattice constant single crystal substrates to produce LaAlO3/SrTiO3 interfaces with controlled levels of biaxial epitaxial strain. We have found that tensile strained SrTiO3 destroys the conducting 2DEG, while compressively strained SrTiO3 retains the 2DEG, but with a carrier concentration reduced in comparison to the unstrained LaAlO3/SrTiO3 interface. We have also found that the critical LaAlO3 overlayer thickness for 2DEG formation increases with SrTiO3 compressive strain. Our first-principles calculations suggest that a strain-induced electric polarization in the SrTiO3 layer is responsible for this behavior. It is directed away from the interface and hence creates a negative polarization charge opposing that of the polar LaAlO3 layer. This both increases the critical thickness of the LaAlO3 layer, and reduces carrier concentration above the critical thickness, in agreement with our experimental results. Our findings suggest that epitaxial strain can be used to tailor 2DEGs properties of the LaAlO3/SrTiO3 heterointerface