A mechanistic rationalization of unusual kinetic behavior in proline-mediated C-O and C-N bond-forming reactions

Kinetic evidence supports the role of the reaction product in the catalytic cycle of proline-mediated alpha-aminoxylation and alpha-amination reactions, providing both design principles as well as a model for the evolution of efficiency in catalysis.     

X-Ray crystallographic and EPR spectroscopic characterization of a pyrrolidine adduct of Y3N@C80

Crystallographic data for the pyrrolidine adduct Y3N@C80C4H9N x 2.5CS2 reveals a slightly pyramidalized Y3N unit with idealized mirror symmetry that straddles the site of addition but does not directly interact with the addend.     

A high power hybrid mid-IR laser source

An efficient hybrid mid-IR laser system comprising a thulium fibre laser, Ho:YAG solid state laser and a zinc germanium phosphide optical parametric oscillator is presented. A 790 nm diode pumped 1908 nm thulium fibre laser operating at 30 W pumps an RTP q-switched Ho:YAG laser emitting 17 W at 40 kHz and 2090 nm. The zinc germanium phosphide optical parametric oscillator efficiently converts this into the 3-5 μm region producing 10.1 W with 59% optical conversion efficiency and an M² = 1.5.     

Role of sub-surface oxygen in Cu(100) oxidation

Density functional theory (DFT) calculations are used to investigate the role of sub-surface oxygen in Cu(100) oxidation. We find that the presence of sub-surface oxygen atoms causes the top copper layer of the missing-row reconstructed surface to rise by 1.7 Å compared to the bare surface. This prediction compares well to an earlier scanning tunneling microscopy measurement of 1.8 Å [Lampimaki et al. Journal of Chemical Physics 126 (2007) 034703]. When the missing-row reconstructed surface is exposed to an additional oxygen molecule, surface restructuring that leads to oxide-like structures is only observed when sub-surface oxygen is present. The oxide-like nature of these structures is confirmed through structural, Bader, and electron density of states analyses. These findings, combined with our previous DFT results that predicted low energy barriers for the embedment of oxygen atoms into the sub-surface [Lee and McGaughey, Surface Science 603 (2009) 3404], demonstrate the key role played by sub-surface oxygen in Cu(100) oxidation.     

640 Gbits/s photonic logic gates

We demonstrate 640 Gbits/s all-optical A AND B, and ā AND B logic functions using pump depletion in a periodically poled lithium niobate waveguide. Bit-error-rate measurements show the effectiveness of the scheme, with a penalty of <2 dB.     

Near-surface turbulence in the atmospheric boundary layer

Measurements of the near-surface turbulence in the atmospheric boundary layer have been made using hot-wire probes above the salt flats of northwestern Utah, where the momentum thickness Reynolds number, R_θ, is O(10⁶), and the surface is smooth and nearly devoid of flow obstructions. The measurements were made with arrays of up to 24 parallel straight sensors and with a modular 12-sensor probe capable of measuring all of the components of the instantaneous velocity vector and velocity gradient tensor. Measurements were also made in a laboratory wind tunnel at R_θ=1730 using 22 straight sensors. The data analysis focuses on the effects of the Reynolds number on turbulence properties and on the physics of the dissipation rate of turbulent kinetic energy.Some properties are found to be dependent on the Reynolds number when normalized with inner variables, while others are not. Among those that show the significant Reynolds number dependence are the rms and the skewness factor of the streamwise velocity fluctuations.Significant differences in flow structure, particularly those related to high rates of dissipation, are implied by the data. The joint PDF and covariance integrand of streamwise and wall normal vorticity fluctuations show less preferred orientation of the vorticity vector in the buffer layer at R_θ of O(10⁶) than at R_θ=1070. The largest contribution to the dissipation rate, at O(10⁶) is by the ∂w/∂z velocity gradient, while this term makes a quite small contribution to the dissipation rate at low R_θ. Here w and z are the spanwise velocity fluctuations and direction, respectively. Conditional analysis in the streamwise-wall normal (x−y) plane based on high instantaneous dissipation rate shows that the typical high dissipation rate events are generally similar at high and low Reynolds numbers, but display some significant differences.     

Extended Antipodal Theorems

In infinite-dimensional Hilbert spaces, we prove that the iterative sequence generated by the extragradient method for solving pseudo-monotone variational inequalities converges weakly to a solution. A class of pseudo-monotone variational inequalities is considered to illustrate the convergent behavior. The result obtained in this note extends some recent results in the literature; especially, it gives a positive answer to a question raised in Khanh (Acta Math Vietnam 41:251–263, 2016).