A paradigm shift in rate determining step from single electron transfer between phenylsulfinylacetic acids and iron(III) polypyridyl complexes to nucleophilic attack of water to the produced sulfoxide radical cation: a non‐linear Hammett

Mechanism of oxidative decarboxylation of phenylsulfinylacetic acids (PSAAs) by iron(III) polypyridyl complexes in aqueous acetonitrile medium has been investigated spectrophotometrically. An initial intermediate formation between PSAA and [Fe(NN)₃]³⁺ is confirmed from the observed Michaelis–Menten kinetics and fractional order dependence on PSAA. Significant rate retardation with concentration of [Fe(NN)₃]³⁺ is rationalized on the basis of coordination of a water molecule at the carbon atom adjacent to the ring nitrogen of the metal polypyridyl complexes by nucleophilic attack at higher concentrations. Electron‐withdrawing and electron‐releasing substituents in PSAA facilitate the reaction and Hammett correlation gives an upward ‘V’ shaped curve. The apparent upward curvature is rationalized based on the change in the rate determining step from electron transfer to nucleophilic attack, by changing the substituents from electron‐releasing to electron‐withdrawing groups. Electron‐releasing substituents in PSAA accelerate the electron transfer from PSAA to the complex and also stabilize the intermediate through resonance interaction leading to negative reaction constants (ρ). Conversely, electron‐withdrawing groups, while retarding the electron transfer exert an accelerating effect on the nucleophilic attack of H₂O which leading to low magnitude of ρ⁺ compared to high ρ^? values of electron‐releasing groups. Marcus theory is applied, and a fair agreement is seen with the experimental values. Copyright © 2016 John Wiley & Sons, Ltd.     

Small-scale fracture toughness of ceramic thin films: the effects of specimen geometry,ion beam notching and high temperature on chromium nitride toughness evaluation

For the implementation of thin ceramic hard coatings into intensive application environments, the fracture toughness is a particularly important material design parameter. Characterisation of the fracture toughness of small-scale specimens has been a topic of great debate, due to size effects, plasticity, residual stress effects and the influence of ion penetration from the sample fabrication process. In this work, several different small-scale fracture toughness geometries (single-beam cantilever, double-beam cantilever and micro-pillar splitting) were compared, fabricated from a thin physical vapour-deposited ceramic film using a focused ion beam source, and then the effect of the gallium-milled notch on mode I toughness quantification investigated. It was found that notching using a focused gallium source influences small-scale toughness measurements and can lead to an overestimation of the fracture toughness values for chromium nitride (CrN) thin films. The effects of gallium ion irradiation were further studied by performing the first small-scale high-temperature toughness measurements within the scanning electron microscope, with the consequence that annealing at high temperatures allows for diffusion of the gallium to grain boundaries promoting embrittlement in small-scale CrN samples. This work highlights the sensitivity of some materials to gallium ion penetration effects, and the profound effect that it can have on fracture toughness evaluation.     

Phased array focusing with guided waves in a viscoelastic coated hollow cylinder

Guided wave phased array focusing has shown many advantages in long-range pipeline inspection, such as, longer inspection distance, greater wave penetration power and higher detection resolution. Viscoelastic coatings applied to a large percentage of pipes for protection purposes created some challenges in terms of focusing feasibility and inspection ability. Previous studies were all based on bare pipe models. In this work, guided wave phased array focusing in viscoelastic coated pipes is studied for the first time. Work was carried out with both numerical and experimental methods. A three-dimensional finite element model was developed for quantitatively and systematically modeling guided waves in pipes with different viscoelastic materials. A method of transforming measured coating properties to finite element method inputs was created in order to create a physically based model of guided waves in coated pipes. Guided wave focusing possibilities in viscoelastic coated pipes and the effects from coatings were comprehensively studied afterwards. A comparison of focusing and nonfocusing inspections was also studied quantitatively in coated pipe showing that focusing increased the wave energy and consequently the inspection ability tremendously. This study provides an important base line and guidance for guided wave propagation and focusing in a real field pipeline under various coating and environmental conditions.     

Real-time detection of DNA interactions with long-period fiber-grating-based biosensor

Using an optical biosensor based on a dual-peak long-period fiber grating, we have demonstrated the detection of interactions between biomolecules in real time. Silanization of the grating surface was successfully realized for the covalent immobilization of probe DNA, which was subsequently hybridized with the complementary target DNA sequence. It is interesting to note that the DNA biosensor was reusable after being stripped off the hybridized target DNA from the grating surface, demonstrating a function of multiple usability.     

Characterization of ammonia two-photon laser-induced fluorescence for gas-phase diagnostics

Two-photon laser-induced fluorescence (LIF) of ammonia (NH₃) with excitation of the C′-X transition at 304.8 nm and fluorescence detection in the 565 nm C′-A band has been investigated, targeting combustion diagnostics. The impact of laser irradiance, temperature, and pressure has been studied, and simulation of NH₃-spectra, fitted to experimental data, facilitated interpretation of the results. The LIF-signal showed quadratic dependence on laser irradiance up to 2 GW/cm². Stimulated emission, resulting in loss of excited molecules, is induced above 10 GW/cm², i.e., above irradiances attainable for LIF imaging. Maximum LIF-signal was obtained for excitation at the 304.8 nm bandhead; however, lower temperature sensitivity over the range 400–700 K can be obtained probing lines around 304.9 nm. A decrease in fluorescence signal was observed with pressure up to 5 bar absolute and attributed to collisional quenching. A detection limit of 800 ppm, at signal-to-noise ratio 1.5, was identified for single-shot LIF imaging over an area of centimeter scale, whereas for single-point measurements, the technique shows potential for sub-ppm detection. Moreover, high-quality NH₃-imaging has been achieved in laminar and turbulent premixed flames. Altogether, two-photon fluorescence provides a useful tool for imaging NH₃-detection in combustion diagnostics.     

Revealing Bell’s nonlocality for unstable systems in high energy physics

Entanglement and its consequences—in particular the violation of Bell inequalities, which defies our concepts of realism and locality—have been proven to play key roles in Nature by many experiments for various quantum systems. Entanglement can also be found in systems not consisting of ordinary matter and light, i.e. in massive meson–antimeson systems. Bell inequalities have been discussed for these systems, but up to date no direct experimental test to conclusively exclude local realism was found. This mainly stems from the fact that one only has access to a restricted class of observables and that these systems are also decaying. In this Letter we put forward a Bell inequality for unstable systems which can be tested at accelerator facilities with current technology. Herewith, the long awaited proof that such systems at different energy scales can reveal the sophisticated “dynamical” nonlocal feature of Nature in a direct experiment gets feasible. Moreover, the role of entanglement and CP\mathcal{CP} violation, an asymmetry between matter and antimatter, is explored, a special feature offered only by these meson–antimeson systems.     

Influence of age and sex on aortic distensibility assessed by MRI in healthy subjects

Magnetic resonance imaging (MRI) is particularly well adapted to the evaluation of aortic distensibility. The calculation of this parameter, based on the change in vessel cross-sectional area per unit change in blood pressure, requires precise delineation of the aortic wall on a series of cine-MR images. Firstly, the study consisted in validating a new automatic method to assess aortic elasticity. Secondly, aortic distensibility was studied for the ascending and descending thoracic aortas in 26 healthy subjects. Two homogeneous groups were available to evaluate the influence of sex and age (with an age limit value of 35 years). The automatic postprocessing method proved to be robust and reliable enough to automatically determine aortic distensibility, even on artefacted images. In the 26 healthy volunteers, a marked decrease in distensibility appears with age, although this decrease is only significant for the ascending aorta (8.97±2.69 10⁻³ mmHg⁻¹ vs. 5.97±2.02 10⁻³ mmHg⁻¹). Women have a higher aortic distensibility than men but only significantly at the level of the descending aorta (7.20±1.61 10⁻³ mmHg⁻¹ vs. 5.05±2.40 10⁻³ mmHg⁻¹). Through our automatic contouring method, the aortic distensibility from routine cine-MRI has been studied on a healthy subject population providing reference values of aortic stiffness. The aortic distensibility calculation shows that age and sex are causes of aortic stiffness variations in healthy subjects.     

SICs and Algebraic Number Theory

We give an overview of some remarkable connections between symmetric informationally complete measurements (SIC-POVMs, or SICs) and algebraic number theory, in particular, a connection with Hilbert’s 12th problem. The paper is meant to be intelligible to a physicist who has no prior knowledge of either Galois theory or algebraic number theory.