High-resolution discrete absorption spectrum of alpha-methallyl free radical in the vapor phase

The alpha-methallyl free radical is formed in the flash photolysis of 3-methylbut-1-ene, and cis-pent-2-ene in the vapor phase, and then subsequent reactions have been investigated by kinetic spectroscopy and gas-liquid chromatography. The photolysis flash was of short duration and it was possible to follow the kinetics of the radicals' decay, which occurred predominantly by bimolecular recombination. The measured rate constant for the alpha-methallyl recombination was (3.5+/-0.3) x 10(10) mol(-1) ls(-1) at 295+/-2K. The absolute extinction coefficients of the alpha-methallyl radical are calculated from the optical densities of the absorption bands. Detailed analysis of related absorption bands and lifetime measurements in the original alpha-methallyl high-resolution discrete absorption spectrum image were also carried out by image processing techniques.     

Optimal ship navigation with safety distance and realistic turn constraints

We consider the optimal ship navigation problem wherein the goal is to find the shortest path between two given coordinates in the presence of obstacles subject to safety distance and turn-radius constraints. These obstacles can be debris, rock formations, small islands, ice blocks, other ships, or even an entire coastline. We present a graph-theoretic solution on an appropriately-weighted directed graph representation of the navigation area obtained via 8-adjacency integer lattice discretization and utilization of the A^∗ algorithm. We explicitly account for the following three conditions as part of the turn-radius constraints: (1) the ship’s left and right turn radii are different, (2) ship’s speed reduces while turning, and (3) the ship needs to navigate a certain minimum number of lattice edges along a straight line before making any turns. The last constraint ensures that the navigation area can be discretized at any desired resolution. Once the optimal (discrete) path is determined, we smoothen it to emulate the actual navigation of the ship. We illustrate our methodology on an ice navigation example involving a 100,000 DWT merchant ship and present a proof-of-concept by simulating the ship’s path in a full-mission ship handling simulator.     

Glass‐embedded silver nanoparticle patterns by masked ion‐exchange process for surface‐enhanced Raman scattering

Glass‐embedded silver nanoparticle patterns were fabricated by masked silver–sodium ion‐exchange process followed by etching to reveal the particles for surface‐enhanced Raman scattering (SERS). The intensity of the enhanced Raman signal is comparable to that of the fluorescence, and the detection limit of 1 nM for Rhodamine 6G has been achieved. Raman images at different etching depths and corresponding morphological images are compared to find optimal SERS signal. Our results demonstrate that silver nanoparticle patterns embedded in glass can be used as SERS‐active substrates. Nanoparticles can be formed in a glass of high optical quality and have potential to be integrated with optical waveguides for a sensor chip. Copyright © 2010 John Wiley & Sons, Ltd.     

Some existence results about radial graphs of constant mean curvature with boundary in parallel planes

In this work, for given H, we investigate the existence of radial cmc H annulus spanning two given non necessarily convex Jordan curves in parallel planes of . We established some existence results under hypotheses relating the geometry of the curves and the distance between the planes. Ari J. Aiolfi was partially supported by Fapergs and Programa FIPE Junior/UFSM.     

Measuring experimental cyclohexane-water distribution coefficients for the SAMPL5 challenge

Small molecule distribution coefficients between immiscible nonaqueuous and aqueous phases—such as cyclohexane and water—measure the degree to which small molecules prefer one phase over another at a given pH. As distribution coefficients capture both thermodynamic effects (the free energy of transfer between phases) and chemical effects (protonation state and tautomer effects in aqueous solution), they provide an exacting test of the thermodynamic and chemical accuracy of physical models without the long correlation times inherent to the prediction of more complex properties of relevance to drug discovery, such as protein-ligand binding affinities. For the SAMPL5 challenge, we carried out a blind prediction exercise in which participants were tasked with the prediction of distribution coefficients to assess its potential as a new route for the evaluation and systematic improvement of predictive physical models. These measurements are typically performed for octanol-water, but we opted to utilize cyclohexane for the nonpolar phase. Cyclohexane was suggested to avoid issues with the high water content and persistent heterogeneous structure of water-saturated octanol phases, since it has greatly reduced water content and a homogeneous liquid structure. Using a modified shake-flask LC-MS/MS protocol, we collected cyclohexane/water distribution coefficients for a set of 53 druglike compounds at pH 7.4. These measurements were used as the basis for the SAMPL5 Distribution Coefficient Challenge, where 18 research groups predicted these measurements before the experimental values reported here were released. In this work, we describe the experimental protocol we utilized for measurement of cyclohexane-water distribution coefficients, report the measured data, propose a new bootstrap-based data analysis procedure to incorporate multiple sources of experimental error, and provide insights to help guide future iterations of this valuable exercise in predictive modeling.     

Highly enantioselective conjugate addition of thiols using mild scandium triflate catalysis

A Sc complex of (4S,5S)-diphenyl PYBOX 1 was found to serve as a catalyst for the asymmetric conjugate addition reactions between various thiols and 3-crotonoyl-2-oxazolidinone, affording the corresponding adducts in good yields and high enantioselectivies (up to 92% ee). A new improved method for making (4S,5S)-diphenyl PYBOX is presented.     

Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.