Enantioselective Brønsted base catalysis with chiral cyclopropenimines

Cyclopropenimines are shown to be a highly effective new class of enantioselective Br?nsted base catalysts. A chiral 2,3-bis(dialkylamino)cyclopropenimine catalyzes the rapid Michael reaction of a glycine imine substrate with high levels of enantioselectivity. A preparative scale reaction to deliver 25 g of product is demonstrated, and a trivial large scale synthesis of the optimal catalyst is shown. In addition, the basicity of a 2,3-bis(dialkylamino)cyclopropenimine is measured for the first time and shown to be approximately equivalent to the P(1)-tBu phosphazene base. An X-ray crystal structure of the protonated catalyst is shown along with a proposed mechanistic and stereochemical rationale.     

Repeated congestion games with bounded rationality

We consider a repeated congestion game with imperfect monitoring. At each stage, each player chooses to use some facilities and pays a cost that increases with the congestion. Two versions of the model are examined: a public monitoring setting where agents observe the cost of each available facility, and a private monitoring one where players observe only the cost of the facilities they use. A partial folk theorem holds: a Pareto-optimal outcome may result from selfish behavior and be sustained by a belief-free equilibrium of the repeated game. We prove this result assuming that players use strategies of bounded complexity and we estimate the strategic complexity needed to achieve efficiency. It is shown that, under some conditions on the number of players and the structure of the game, this complexity is very small even under private monitoring. The case of network routing games is examined in detail.     

New cosmic microwave background constraint to primordial gravitational waves

Primordial gravitational waves (GWs) with frequencies > or approximately equal to 10(-15) Hz contribute to the radiation density of the Universe at the time of decoupling of the cosmic microwave background (CMB). This affects the CMB and matter power spectra in a manner identical to massless neutrinos, unless the initial density perturbation for the GWs is nonadiabatic, as may occur if such GWs are produced during inflation or some post-inflation phase transition. In either case, current observations provide a constraint to the GW amplitude that competes with that from big-bang nucleosynthesis (BBN), although it extends to much lower frequencies (approximately 10(-15) Hz rather than the approximately 10(-10) Hz from BBN): at 95% confidence level, omega(gw)h(2) 相似文献   

Role of Hydrogen Bond Defects for Cluster Formation and Distribution in Ionic Liquids by Means of Neutron Diffraction and Molecular Dynamics Simulations

Defects fundamentally govern the properties of all real materials. Correlating molecular defects to macroscopic quantities remains a challenge, particularly in the liquid phase. Herein, we report the influence of hydrogen bonds (HB) acting as defects in mixtures of non-hydroxyl-functionalized ionic liquids (ILs) with an increasing concentration of hydroxyl-functionalized ILs. We observed two types of HB defects: The conventional HBs between cation and anion (c–a), and the elusive HBs between cations (c–c) despite the repulsive Coulomb forces. We use neutron diffraction with isotopic substitution in combination with molecular dynamics simulations for measuring the geometry, strength, and distribution of mobile OH defects in the IL mixtures. In principle, this procedure allows relating the number and stability of defects to macroscopic properties such as diffusion, viscosity, and conductivity, which are of utmost importance for the performance of electrolytes in batteries and other electrical devices.