Magnetooptical, electrooptical and photoelastic effects in an elastic polarizable and magnetizable isotropic continuum

The magnetooptical, electrooptical and photoelastic behaviour of an elastic polarizable and magnetizable isotropic continuum are investigated from a dynamical point of view, starting from balance equations and constitutive relations. The most original result of the theory is the fact that the continuum exhibits the Cotton-Mouton effect, together with linear birefringence of transverse sound waves. This is compared with experimental data and quantum theory results.As expected, the continuum does not exhibit Faraday rotation.     

A caged lanthanide complex as a paramagnetic shift agent for protein NMR

A lanthanide complex, named CLaNP (caged lanthanide NMR probe) has been developed for the characterisation of proteins by paramagnetic NMR spectroscopy. The probe consists of a lanthanide chelated by a derivative of DTPA (diethylenetriaminepentaacetic acid) with two thiol reactive functional groups. The CLaNP molecule is attached to a protein by two engineered, surface-exposed, Cys residues in a bidentate manner. This drastically limits the dynamics of the metal relative to the protein and enables measurements of pseudocontact shifts. NMR spectroscopy experiments on a diamagnetic control and the crystal structure of the probe-protein complex demonstrate that the protein structure is not affected by probe attachment. The probe is able to induce pseudocontact shifts to at least 40 A from the metal and causes residual dipolar couplings due to alignment at a high magnetic field. The molecule exists in several isomeric forms with different paramagnetic tensors; this provides a fast way to obtain long-range distance restraints.     

Efficient energy conversion for cubic third-harmonic generation that is phase matched in KTiOPO(4)

We demonstrate, for the first time to our knowledge, that efficient third-harmonic generation can be achieved with a cubic contribution much larger than the quadratic processes. An energy-conversion efficiency of 2.4% is achieved for cubic third-harmonic generation that is phase matched along the x axis of a KTiOPO(4) crystal by use of a picosecond fundamental laser emitting at 1618 nm. The associated cascading processes are only 10% of the pure cubic interaction, which is very suitable for study of the specific quantum optical correlations. Calculations of the third-harmonic generation conversion efficiency with respect to group-velocity dispersion and to the longitudinal Gaussian beam profile account well for our experimental results.     

Disclinated states in nematic elastomers

We present a theory for uniaxial nematic elastomers with variable asphericity. As an application of the theory, we consider the time-independent, isochoric radial expansion of a right circular cylinder. Numerical solutions to the resulting differential equation are obtained for a range of radial expansions. For all expansions considered, there exists an isotropic core of material surrounding the cylinder axis where the asphericity vanishes and in which the polymeric chains are shaped as spherical coils. This region, corresponding to a disclination of strength +1 along the axis, is bounded by a narrow transition layer across which the asphericity increases rapidly and attains a non-trivial positive value. The material thereby becomes anisotropic away from the disclination so that the polymeric chains are shaped as ellipsoidal coils of revolution prolate about the cylinder radius. In accordance with the area of steeply changing asphericity between isotropic and anisotropic regimes, a marked drop in the free-energy density is observed. The boundary of the disclination core is associated with the location of this energy drop. For realistic choices of material parameters, this criterion yields a core on the order of 10⁻² μm, which coincides with observations in conventional liquid-crystal melts. Also occurring at the core boundary, and further confirming its location, are sharp transitions in the behavior of the constitutively determined contributions to the deformational stress and a change in the pressure. Furthermore, the constitutively determined contribution to the orientational stress is completely concentrated at the core boundary. The total energy shows a definitive preference for disclinated states.     

Stability of a two-phase process in an elastic solid

This work investigates the linear stability of an antiplane shear motion which involves a steadily propagating normal planar phase boundary in an arbitrary element of a family of non-elliptic generalized neo-Hookean materials. It is shown that such a process is linearly unstable with respect to a large class of disturbances if and only if the kinetic response function—a constitutively supplied entity which relates the normal velocity of a phase boundary to the driving traction which acts on it—is locally decreasing as a function of the appropriate argument. This result holds whether or not inertial effects are taken into consideration, demonstrating that the linear stability of the relevant process depends entirely upon the transformation kinetics intrinsic to the kinetic response function. The morphological evolution of the interface is then, in an inertia-free setting, tracked for a short time subsequent to the perturbation. It is found that, when the kinetic response function is non-monotonic, the phase boundary can evolve so as to qualitatively resemble the plate-like structures which are found in displacive solid-solid phase transformations.     

Improvement of the decision efficiency of the accuracy profile by means of a desirability function for analytical methods validation. Application to a diacetyl-monoxime colorimetric assay used for the determination of urea in transdermal iontophoretic extracts

Validation of analytical methods is a widely used and regulated step for each analytical method. However, the classical approaches to demonstrate the ability to quantify of a method do not necessarily fulfill this objective. For this reason an innovative methodology was recently introduced by using the tolerance interval and accuracy profile, which guarantee that a pre-defined proportion of future measurements obtained with the method will be included within the acceptance limits. Accuracy profile is an effective decision tool to assess the validity of analytical methods. The methodology to build such a profile is detailed here. However, as for any visual tool it has a part of subjectivity. It was then necessary to make the decision process objective in order to quantify the degree of adequacy of an accuracy profile and to allow a thorough comparison between such profiles. To achieve this, we developed a global desirability index based on the three most important validation criteria: the trueness, the precision and the range. The global index allows the classification of the different accuracy profiles obtained according to their respective response functions. A diacetyl-monoxime colorimetric assay for the determination of urea in transdermal iontophoretic extracts was used to illustrate these improvements.     

Ternary molybdenum cluster sulfides: electrochemical and chemical behavior of in situ pulsed laser deposited thin films

The electrochemical deinsertions and insertions in recently synthesised PLD molybdenum cluster sulfide films are presented. We prove that Cu_xMo₆S₈ can be electrochemically converted to Mo₆S₈. The copper, cadmium, zinc and lead intercalation performed by electrochemistry on deintercalated films has succeeded. During this study, we also report that the use of a chemical process allows the formation of PbMo₆S₈ and SnMo₆S₈ thin films, that means that the intercalation of large cations is effective like the one of small cations.     

Resonant soft X-ray scattering in polymer science

Resonant soft X-ray scattering (RSoXS) is an emerging, powerful technique to probe the nano-to-mesoscale structure of polymers and other molecules. It joins together small-angle X-ray scattering (a statistical nanoprobe) with X-ray spectroscopy that brings with it unique chemical and bond-orientation sensitivity. Through over a decade of discovery and development, RSoXS is moving from a niche technique applied to organic electronic thin films to a mature tool applicable to a plethora of polymeric and molecular systems, encompassing new modalities, analyses, and simulation methods. This development promises to deliver increasingly quantitative answers to challenging questions in polymer science as well as expand its usefulness to complementary fields. This review presents a full synopsis of the technique, including background on the theoretical underpinnings, measurement best practices, and examples of recent RSoXS applications and discoveries provided here to accelerate the transition to a broader range of soft matter and polymeric fields.     

Amorphous copolyesters based on bibenzoic acids and neopentyl glycol

High T_g amorphous copolyester thermoplastics were synthesized by incorporating 4,4′‐bibenzoate (4,4′BB) and 3,4′‐bibenzoate moieties into the polyester backbone via melt polycondensation. The high levels of crystallinity typically associated with 4,4′BB containing polyesters were suppressed through copolymerization of ethylene glycol, 1,4‐cyclohexane dimethanol, and neopentyl glycol (NPG) diols. NPG was shown to be highly effective in suppressing crystallization and was used to produce amorphous compositions with T_g’s as high as 129 °C. Diol ratios were determined by ¹H NMR spectroscopy and molecular weights were assessed with inherent viscosity (η_inh). Thermogravimetric analysis showed single‐step weight losses in the range of 395 – 419 °C. Differential scanning calorimetry was used to determine melting points and glass transition temperatures over a wide range of copolyester compositions and identified amorphous compositions. Dynamic mechanical analysis confirmed T_g’s and was used to study β‐relaxations below the T_g. Rheological analysis revealed the effect of NPG structures on shear thinning and thermal stability. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 579–587