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.     

Noninvasive Temperature Measurement in Dental Materials Using Nd3+, Yb3+ Doped Nanoparticles Emitting in the Near Infrared Region

In this work, the application of near infrared (NIR)-emitting NaYbF₄:1%Tm³⁺@NaLuF₄:30%Nd³⁺ core–shell nanoparticles is reported for noninvasive probing and monitoring the temperature during photopolymerization of dental materials. When excited at 808 nm, the synthesized nanoparticles emit NIR photoluminescence (PL) with two distinctive peaks at 865 and 980 nm which correspond to radiative transitions from the doped Nd³⁺ and Yb³⁺ ions, respectively. Luminescence intensity ratio between these two bands is found to vary with temperature due to temperature-dependent electronic excitation energy transfer between Nd³⁺ and Yb³⁺ ions at the core/shell interface. This finding allows luminescence ratiometric evaluation of the in situ temperature during photopolymerization of resin cement (doped with nanoparticles) in a veneer placement procedure. In addition, the NIR emission also enables PL imaging of the distribution of the adhesive under the veneer. The results highlight that rare-earth ions–doped nanoparticles with both excitation and emission in the NIR spectral range are advantageous for both PL-based nanothermometry and imaging due to the reduced attenuation of NIR light by dental ceramics.     

An immersed boundary method wall model for high‐Reynolds‐number channel flow over complex topography

High‐Reynolds‐number channel flows regularly encounter topographies composed of multiple length scales and that protrude into the boundary layer. Physically, the presence of immersed obstacles leads to increased velocity gradients, turbulence production, and manifestation of wakes. Considerable challenges are associated with numerically describing the presence of obstacles in channel flows. Common approaches include generation of a computational mesh that is uniquely designed for the flow and obstacle, the immersed boundary method, and terrain‐following coordinates. There are challenges and limitations associated with each of these techniques. Specification of boundary conditions representing the perimeter of solid obstacles is a primary challenge of the immersed boundary method. In this document, a simplistic canopy stress‐like wall model is used to impose boundary conditions. The model isolates aerodynamically relevant local frontal areas through evaluation of the gradient of the topographic height field. The gradient of the height field describes both the surface‐normal direction and the frontal area, making it ideal for detecting areas on which the flow impinges. The model is tested in numerical simulations of turbulent half‐channel flow over topographies with different obstacles affixed–right prisms, rectangular prisms, ellipsoidal mounds, and sinusoids. In all cases, the performance is strong relative to datasets presented in the literature. Results are finally presented for numerical simulation of flow over complex synthetic fractal‐like topography and a synthetic city. These results show interesting trends in how the turbulent multiscale flow field responds to multiscale topography. Copyright © 2012 John Wiley & Sons, Ltd.     

MASS TRANSFER EXPERIMENTS ON SINGLE IRREGULAR-SHAPED PARTICLES

Mass transfer from irregular-shaped naphthalene particles (100-200 inn in size) was studitd in an electrodynamic balance. Charged particles were suspended in an electrostatic field directly in line with a calibrated air jet. Mass and size change histories were obtained under ambient conditions, and under steady- and pulsed-flow conditions. For natural convection, the time-averaged Sherwood number was similar to that for spheres. Forced-convection Sherwood number under steady-flow conditions was strongly dependent on particle shape and panicle Reynolds number, and was consistently higher than values predicted for spheres at comparable Reynolds numbers. This study validates the technique and indicates the shape effect on mass transfer form single particles.     

Total synthesis of amorfrutin A via a palladium-catalyzed migratory prenylation–aromatization sequence

The total synthesis of amorfrutin A, a prenyl bibenzyl natural product has been achieved in five steps from 2,2,6-trimethyl-4H-1,3-dioxin-4-one. The key step of the synthesis is an efficient palladium(0)-catalyzed decarboxylative prenylation migration and aromatization sequence.     

Multiscale expansions in discrete world

In this paper, we show the attainability of KdV equation from some types of nonlinear Schrödinger equation by using multiscale expansions discretely. The power of this manageable method is confirmed by applying it to two selected nonlinear Schrödinger evolution equations. This approach can also be applied to other nonlinear discrete evolution equations. All the computations have been made with Maple computer packet program.     

A Simple Proof of the Sharp Weighted Estimate for Calderón–Zygmund Operators on Homogeneous Spaces

Here we show that Lerner’s method of local mean oscillation gives a simple proof of the A ₂ conjecture for spaces of homogeneous type, that is, the linear dependence on the A ₂ norm for weighted L ² Calderón–Zygmund operator estimates. In the Euclidean case, the result is due to Hytönen, and for geometrically doubling spaces, Nazarov, Reznikov, and Volberg obtained the linear bound.