Synthesis and characterization of a new red-emitting Ca2+ indicator, calcium ruby

Calcium Ruby m-Cl (X = H, Y = Cl) is a visible-light excited red-emitting calcium concentration ([Ca2+]) indicator dye (579/598 nm peak excitation/emission) with a side arm for conjugation via EDC or click chemistry. Its large molar extinction and high quantum yield rank it among the brightest long-wavelength Ca2+ indicators. Calcium Ruby is a promising alternative to existing dyes for imaging [Ca2+] in multicolor fluorescence applications or in the presence of yellow-green cellular autofluorescence.     

Novel functionalized pyridine-containing DTPA-like ligand. Synthesis, computational studies and characterization of the corresponding Gd(III) complex

A novel pyridine-containing DTPA-like ligand, carrying additional hydroxymethyl groups on the pyridine side-arms, was synthesized in 5 steps. The corresponding Gd(III) complex, potentially useful as an MRI contrast agent, was prepared and characterized in detail by relaxometric methods and its structure modeled by computational methods.     

High-sensitivity laser-based ultrasonic C-scan system for materials inspection

A beam-steering C-scan system for laser generation and detection of ultrasound in opaque solids has been developed. For ultrasound detection, the system uses a confocal Fabry-Perot interferometer that is stabilized at its high-sensitivity point by implementing a novel procedure that does not require a reference beam. This stabilization procedure effectively compensates for slowly varying (up to 2 Hz) disturbances and, more important, for any change in the interferometer illumination conditions while probing different scanning points. For the latter reason, the proposed stabilization appears to be more effective than previous approaches for high-sensitivity ultrasound detection in beamsteering scans. Noise performance and sensitivity limit of the system are evaluated. Ultrasonic echoes are detected in aluminum samples having optically rough surfaces with single-pulse generation signal-to-noise ratios on the order of 20 dB. A C-scan inspection is performed where a known defect in the test piece is successfully detected by time-of-flight gating of the ultrasonic signals.     

On the evaluation of the anisotropic-isotropic transition volume fraction for a semirigid polymer

It has been found that a method allowing the calculation of an anisotropic-isotropic transition volume fraction for a given semirigid polymer can be derived from the equations recently proposed by Blonski and coworkers to evaluate the equilibrium compositions of isotropic and anisotropic phases coexisting within ternary systems semirigid polymer/flexible polymer/solvent. By using the term anisotropic-isotropic transition volume fraction of a semirigid polymer we will refer to its smallest volume fraction giving an anisotropic character to liquid ternary phases also including a flexible polymer and a solvent. Its evaluation simplifies the construction of the corresponding ternary diagram and can also be seen as a fast and quantitative way of estimating the influence exerted by the semirigid polymer, through its intrinsic anisotropy, on ternary phases.     

Thermal Stress Measurement in Continuous Welded Rails Using the Hole-Drilling Method

The absence of expansion joints in Continuous Welded Rail has created the need for the railroad industry to determine the in-situ thermal stress levels for rail buckling and breakage prevention. This paper explores the hole-drilling method as a possible solution to this problem. A new set of calibration coefficients to compute the stress field relieved by fine hole depth increments required by the high strength steel was determined. The new calibration coefficients were experimentally validated on an aluminum plate subjected to a known uniaxial load. The thermal stress levels of constrained rails were estimated after compensation for the residual stress components, based on statistical relationships developed experimentally between the longitudinal and the vertical residual stresses. The results showed that the hole-drilling procedure, with appropriate calibration coefficients and residual stress compensation, can estimate the in-situ rail thermal stresses with an expected accuracy that is within the industry acceptable levels.     

On the structure of 3‐acetylamino‐5‐methyl‐1,2,4‐oxadiazole and on the fully degenerate rearrangements (FDR) of its anion: a stimulating comparison between the results of ‘in‐silicon chemistry’ and ‘laboratory chemistry’

An accurate crystal structure determination has provided evidence for a planar conformation for 3‐acetylamino‐5‐methyl‐1,2,4‐oxadiazole ( 5 ), in agreement with quantum‐mechanical calculations in the gas phase. In the crystal, a series of strong intermolecular N7H7^….O9 hydrogen bonds link the amido groups of different molecules, causing the formation of infinite parallel ordered chains. The effect of the DMSO solvent on the energy and charge distribution of compound 5 and on its relevant 5 ^? anion, involved in a fully degenerate rearrangement (FDR), has been deepened by quantum‐mechanical DFT calculations. The calculated energy barrier for the FDR increases in going from in vacuo to DMSO, in agreement with previsions based on the Hughes and Ingold rules concerning the nucleophilic substitution of an anionic reagent (the deprotonated amido group in the side chain) on a neutral substrate (the 1,2,4‐oxadiazole ring). Copyright © 2009 John Wiley & Sons, Ltd.     

Molecular Photoacoustic Tomography with Colloidal Nanobeacons

Spotting clots : Vascularly constrained colloidal gold nanobeacons (GNBs; see picture) can be used as exogenous photoacoustic contrast agents for the targeted detection of fibrin, a major biochemical feature of thrombus. Fibrin‐targeted GNBs provide a more than tenfold signal enhancement in photoacoustic tomography in the near‐IR wavelength window, indicating their potential for diagnostic imaging.

     

On the Robin-Transmission Boundary Value Problems for the Nonlinear Darcy–Forchheimer–Brinkman and Navier–Stokes Systems

The purpose of this paper is to study a boundary value problem of Robin-transmission type for the nonlinear Darcy–Forchheimer–Brinkman and Navier–Stokes systems in two adjacent bounded Lipschitz domains in \({{\mathbb{R}}^{n} (n\in \{2,3\})}\), with linear transmission conditions on the internal Lipschitz interface and a linear Robin condition on the remaining part of the Lipschitz boundary. We also consider a Robin-transmission problem for the same nonlinear systems subject to nonlinear transmission conditions on the internal Lipschitz interface and a nonlinear Robin condition on the remaining part of the boundary. For each of these problems we exploit layer potential theoretic methods combined with fixed point theorems in order to show existence results in Sobolev spaces, when the given data are suitably small in \({L^2}\)-based Sobolev spaces or in some Besov spaces. For the first mentioned problem, which corresponds to linear Robin and transmission conditions, we also show a uniqueness result. Note that the Brinkman–Forchheimer-extended Darcy equation is a nonlinear equation that describes saturated porous media fluid flows.     

Nonlinear wave propagation in constrained solids subjected to thermal loads

The classical mathematical treatment governing nonlinear wave propagation in solids relies on finite strain theory. In this scenario, a system of nonlinear partial differential equations can be derived to mathematically describe nonlinear phenomena such as acoustoelasticity (wave speed dependency on quasi-static stress), wave interaction, wave distortion, and higher-harmonic generation. The present work expands the topic of nonlinear wave propagation to the case of a constrained solid subjected to thermal loads. The origin of nonlinear effects in this case is explained on the basis of the anharmonicity of interatomic potentials, and the absorption of the potential energy corresponding to the (prevented) thermal expansion. Such “residual” energy is, at least, cubic as a function of strain, hence leading to a nonlinear wave equation and higher-harmonic generation. Closed-form solutions are given for the longitudinal wave speed and the second-harmonic nonlinear parameter as a function of interatomic potential parameters and temperature increase. The model predicts a decrease in longitudinal wave speed and a corresponding increase in nonlinear parameter with increasing temperature, as a result of the thermal stresses caused by the prevented thermal expansion of the solid. Experimental measurements of the ultrasonic nonlinear parameter on a steel block under constrained thermal expansion confirm this trend. These results suggest the potential of a nonlinear ultrasonic measurement to quantify thermal stresses from prevented thermal expansion. This knowledge can be extremely useful to prevent thermal buckling of various structures, such as continuous-welded rails in hot weather.     

NMR properties of sedimented solutes

This perspective paper is intended to give some insights into the recently proposed technique of NMR of solutes sedimented by ultracentrifugation in a rotor used for solid state NMR experiments. Sedimented "states" correspond to molecules with very little reorientational capability in extremely concentrated solutions. They provide solid state NMR spectra comparable in quality with those of the best microcrystalline samples. Here we report some experiments to look for chemicals which affect the properties of the sediment, and we show that it is possible to fill the rotor in a true ultracentrifuge and then record the spectra. The latter possibility opens new horizons for NMR of sedimented systems.