Spreading of Lagrangian Regularity on Rational Invariant Tori

Let P _h be a self-adjoint semiclassical pseudodifferential operator on a manifold M such that the bicharacteristic flow of the principal symbol on T*M is completely integrable and the subprincipal symbol of P _h vanishes. Consider a semiclassical family of eigenfunctions, or, more generally, quasimodes u _h of P _h . We show that on a nondegenerate rational invariant torus, Lagrangian regularity of u _h (regularity under test operators characteristic on the torus) propagates both along bicharacteristics, and also in an additional “diffractive” manner. In particular, in addition to propagating along null bicharacteristics, regularity fills in the interiors of small annular tubes of bicharacteristics.     

Eigenvalue equalization filtered-x algorithm for the multichannel active noise control of stationary and nonstationary signals

The FXLMS algorithm, which is extensively used in active noise control, exhibits frequency dependent convergence behavior. This leads to degraded performance for time-varying and multiple frequency signals. A new algorithm called the eigenvalue equalization filtered-x least mean squares (EE-FXLMS) has been developed to overcome this limitation without increasing the computational burden of the controller. The algorithm is easily implemented for either single or multichannel control. The magnitude coefficients of the secondary path transfer function estimate are altered while preserving the phase. For a reference signal that has the same magnitude at all frequencies, the secondary path estimate is given a flat response over frequency. For a reference signal that contains tonal components of unequal magnitudes, the magnitude coefficients of the secondary path are adjusted to be the inverse magnitude of the reference tones. Both modifications reduce the variation in the eigenvalues of the filtered-x autocorrelation matrix and lead to increased performance. Experimental results show that the EE-FXLMS algorithm provides 3.5-4.4 dB additional attenuation at the error sensor compared to normal FXLMS control. The EE-FXLMS algorithm's convergence rate at individual frequencies is faster and more uniform than the normal FXLMS algorithm with several second improvement being seen in some cases.     

Controlling thermomechanical behavior of semicrystalline hydrogenated polynorbornene through the cis- to trans-cyclopentylene ratio

Though polynorbornene synthesized by ring-opening metathesis polymerization has an intrinsically all-cis configuration of the cyclopentylene backbone rings, a fraction of these rings can be epimerized to the trans configuration during hydrogenation over suitable catalysts. By varying the method of hydrogenation, semicrystalline hydrogenated polynorbornenes (hPNs) with trans levels between 0 and 36% were obtained. With increasing trans content, the glass transition temperature, melting point, and enthalpy of melting decrease modestly. By contrast, the temperature at which the hPN crystal transitions into a rotationally disordered polymorph varies strongly with trans content, ranging from 126 °C (all-cis) to 71 °C at 27% trans; at trans contents of 34% and above, no rotationally-ordered phase is observed at any temperature. The room-temperature Young's modulus shows no dependence on trans content, while the yield stress drops by 20% at 1% trans content and slowly decreases further with additional epimerization. The temperature dependence of the Young's modulus differs for trans-containing versus all-cis polymers, while the temperature dependence of the yield stress is set by the polymorph type (rotationally ordered vs. disordered).     

Catalytic Behavior of Mono-N-Protected Amino-Acid Ligands in Ligand-Accelerated C−H Activation by Palladium(II)

Mono-N-protected amino acids (MPAAs) are increasingly common ligands in Pd-catalyzed C−H functionalization reactions. Previous studies have shown how these ligands accelerate catalytic turnover by facilitating the C−H activation step. Here, it is shown that MPAA ligands exhibit a second property commonly associated with ligand-accelerated catalysis: the ability to support catalytic turnover at substoichiometric ligand-to-metal ratios. This catalytic role of the MPAA ligand is characterized in stoichiometric C−H activation and catalytic C−H functionalization reactions. Palladacycle formation with substrates bearing carboxylate and pyridine directing groups exhibit a 50–100-fold increase in rate when only 0.05 equivalents of MPAA are present relative to Pd^II. These and other mechanistic data indicate that facile exchange between MPAAs and anionic ligands coordinated to Pd^II enables a single MPAA to support C−H activation at multiple Pd^II centers.     

Chemical immobilization of crosslinked polymeric ionic liquids on nitinol wires produces highly robust sorbent coatings for solid-phase microextraction

Super elastic nitinol (NiTi) wires were exploited as highly robust supports for three distinct crosslinked polymeric ionic liquid (PIL)-based coatings in solid-phase microextraction (SPME). The oxidation of NiTi wires in a boiling (30% w/w) H₂O₂ solution and subsequent derivatization in vinyltrimethoxysilane (VTMS) allowed for vinyl moieties to be appended to the surface of the support. UV-initiated on-fiber copolymerization of the vinyl-substituted NiTi support with monocationic ionic liquid (IL) monomers and dicationic IL crosslinkers produced a crosslinked PIL-based network that was covalently attached to the NiTi wire. This alteration alleviated receding of the coating from the support, which was observed for an analogous crosslinked PIL applied on unmodified NiTi wires. A series of demanding extraction conditions, including extreme pH, pre-exposure to pure organic solvents, and high temperatures, were applied to investigate the versatility and robustness of the fibers. Acceptable precision of the model analytes was obtained for all fibers under these conditions. Method validation by examining the relative recovery of a homologous group of phthalate esters (PAEs) was performed in drip-brewed coffee (maintained at 60 °C) by direct immersion SPME. Acceptable recoveries were obtained for most PAEs in the part-per-billion level, even in this exceedingly harsh and complex matrix.