Multiple-magnetic field 139La NMR and density functional theory investigation of the solid lanthanum(III) halides

Results from a solid-state ¹³⁹La NMR spectroscopic investigation of the anhydrous lanthanum(III) halides (LaX₃; X=F, Cl, Br, I) at applied magnetic fields of 7.0, 9.4, 11.7, 14.1, and 17.6 T are presented and highlight the advantages of working at high applied magnetic field strengths. The ¹³⁹La quadrupolar coupling constants are found to range from 15.55 to 24.0 MHz for LaCl₃ and LaI₃, respectively. The lanthanum isotropic chemical shifts exhibit an inverse halogen dependence with values ranging from −135 ppm for LaF₃ to 700 ppm for LaI₃, which represents nearly half of the total lanthanum chemical shift range. The spans of the magnetic shielding tensors also vary widely, from 35 to 650 ppm for the solid LaF₃ through LaI₃. DFT calculations of the ¹³⁹La electric field gradient and magnetic shielding tensors have been performed and provide a qualitative interpretation of the trends observed experimentally.     

Spectrophotometric determination of ziram (dithiocarbamate fungicide) by thiocyanate and rhodamine 6G method

A sensitive spectrophotometric method has been developed for the determination of ziram in water, vegetables and grains. The method is based on the dissociation of dithiocarbamate complex of zinc with thiocyanate and rhodamine 6G at pH 4 to form a pink coloured complex that is stabilized by gelatin. The method is simple and Beer's law is obeyed over the concentration range of 0.05-1 ppm of ziram. The method is free from interference of similar dithiocarbamate fungicides containing Mn(2+) and Fe(3+) ions.     

Humidity sensor based on a single-mode hetero-core fiber structure

Using a small-core single-mode fiber (SCSMF), a novel relative humidity (RH) sensor based on an SMF28-SCSMF-SMF28 fiber structure was proposed in this paper. By depositing a humidity sensitive material, such as poly (ethylene oxide) (PEO) on the bare SCSMF fiber, the proposed structure can act as an RH sensor with high sensitivity. Experiments demonstrated that the proposed RH sensor with PEO coating can achieve a sensitivity of 430 nm per relative humidity unit (RHU) in the RH range from 80% to 83% RH and a sensitivity of 50 nm per RHU in the RH range from 83% to 95% RH.     

Martingale representation for Poisson processes with applications to minimal variance hedging

We consider a Poisson process η on a measurable space equipped with a strict partial ordering, assumed to be total almost everywhere with respect to the intensity measure λ of η. We give a Clark-Ocone type formula providing an explicit representation of square integrable martingales (defined with respect to the natural filtration associated with η), which was previously known only in the special case, when λ is the product of Lebesgue measure on R₊ and a σ-finite measure on another space X. Our proof is new and based on only a few basic properties of Poisson processes and stochastic integrals. We also consider the more general case of an independent random measure in the sense of Itô of pure jump type and show that the Clark-Ocone type representation leads to an explicit version of the Kunita-Watanabe decomposition of square integrable martingales. We also find the explicit minimal variance hedge in a quite general financial market driven by an independent random measure.     

Chemical failure modes of AlQ3-based OLEDs: AlQ3 hydrolysis

Tris(8-hydroxyquinoline)aluminum(III), AlQ3, is used in organic light-emitting diodes (OLEDs) as an electron-transport material and emitting layer. The reaction of AlQ3 with trace H2O has been implicated as a major failure pathway for AlQ3-based OLEDs. Hybrid density functional calculations have been carried out to characterize the hydrolysis of AlQ3. The thermochemical and atomistic details for this important reaction are reported for both the neutral and oxidized AlQ3/AlQ3+ systems. In support of experimental conclusions, the neutral hydrolysis reaction pathway is found to be a thermally activated process, having a classical barrier height of 24.2 kcal mol(-1). First-principles infrared and electronic absorption spectra are compared to further characterize AlQ3 and the hydrolysis pathway product, AlQ2OH. The activation energy for the cationic AlQ3 hydrolysis pathway is found to be 8.5 kcal mol(-1) lower than for the neutral reaction, which is significant since it suggests a role for charge imbalance in promoting chemical failure modes in OLED devices.     

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.     

Tuning the enantioselective N-acetylation of racemic amines: a spectacular salt effect

We have described a spectacular salt effect in the kinetic resolution of (+/-)-1-phenylethylamine, which leads to an increase in reactivity, high levels of selectivity, and a complete reversal of the stereoselectivity. By tuning the reaction conditions, we were able to increase the selectivity factor of (1S,2S)-1 to s = 115.     

Integral invariants for non-barotropic flows in a four dimensional space time manifold

Properties of non-barotropic flows are described using Lie derivatives of differential forms in a Euclidean four dimensional space-time manifold. Vanishing of the Lie derivative implies that the corresponding physical quantity remains invariant along the integral curves of the flow. Integral invariants of non-barotropic perfect and viscous flows are studied using the concepts of relative and absolute invariance of forms. The four dimensional expressions for the rate of change of the generalized circulation, generalized vorticity flux, generalized helicity and generalized parity in the case of ideal and viscous non-barotropic flows are thereby obtained.     

Nonlocalized modulation of periodic reaction diffusion waves: The Whitham equation

In a companion paper, we established nonlinear stability with detailed diffusive rates of decay of spectrally stable periodic traveling-wave solutions of reaction diffusion systems under small perturbations consisting of a nonlocalized modulation plus a localized (L ¹) perturbation. Here, we determine time-asymptotic behavior under such perturbations, showing that solutions consist of a leading order of a modulation whose parameter evolution is governed by an associated Whitham averaged equation.