Recent trends in perfluorinated sulfoximines

The search for original perfluorinated moieties is a very modern and attractive challenge. Among the emergent groups, the S-perfluoroalkylated sulfoximines are very peculiar because of their structural diversity and promising properties. A literature survey shows that interest in these molecules is strongly increasing. This short review summarizes the recent works devoted to this topic.     

A macroscopic model for magnetic shape-memory single crystals

A rate-independent model for the quasi-static magneto-elastic evolution of a magnetic shape-memory single crystal is presented. In particular, the purely mechanical Souza–Auricchio model for shape-memory alloys is here combined with classical micro-magnetism by suitably associating magnetization and inelastic strain. By balancing the effect of conservative and dissipative actions, a nonlinear evolution PDE system of rate-independent type is obtained. We prove the existence of so-called energetic solutions to this system. Moreover, we discuss several limits for the model corresponding to parameter asymptotics by means of a rigorous Γ-convergence argument.     

A facile synthetic route to new pyrazoloisoindolones

A facile method for the synthesis of new pyrazoloisoindolones via a Suzuki cross-coupling reaction using a pyrazolylboronic ester is described.     

Variational Convergences of Dual Energy Functionals for Elastic Materials with a ε-Thin Strong Inclusion

We give a new derivation, based on the complementary energy formulation, of a simplified model for a multi-structure made up of two anisotropic hyper-elastic bodies connected by a thin strong material layer. The model is obtained by identifying the Mosco-limit of the stored complementary energy functional when the thickness is of order ?? and the stiffness of order 1/?? where ?? is a positive real adimensional parameter. In order to prove the existence of the displacement associated with the stress we use a suitable weak version of the Saint-Venant compatibility condition also known as Donati??s theorem.     

Self assembly of anastomosis-like superstructures in fatty acid/guanidine hydrochloride aqueous dispersions

A mixture between 1% sodium myristate and guanidine hydrochloride at a molar ratio of 1 in water forms a gel of membranes below a phase transition of ca. 21 °C and a viscous limpid and isotropic solution above. As observed by both TEM and AFM, we report the formation of interconnected superstructures in that latter phase. Those assemblies exhibit a size of ca. 4–40 nm width and several tens of μm length with unexpected disconnections and re-connections between them having the appearance of an anastomosis-like superstructure.     

(Vapor + liquid) equilibria of binary mixtures containing light alcohols and ionic liquids

This work presents (vapor + liquid) equilibrium (VLE) of binary mixtures containing methanol or ethanol and three imidazolium based ionic liquids: 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium acetate, and 1-butyl-3-methylimidazolium hydrogen sulfate. VLE measurements were carried out over the whole range of composition between (283.15 and 298.15) K using a static apparatus. Activity coefficients γ_i of these solvents in the ionic liquids have been determined from the VLE data and correlated using the NRTL model. The results show that the NRTL model can be applied successfully with systems containing ionic liquids.     

Spectroscopic, magnetochemical, and crystallographic study of cesium iron phosphate hexahydrate: characterization of the electronic structure of the iron(II) hexa-aqua cation in a quasicubic environment

Spectroscopic, magnetochemical, and crystallographic data are presented for CsFe(H2O)6PO4, a member of a little-known isomorphous series of salts that facilitates the study of hexa-aqua ions in a quasicubic environment. Above 120 K, the deviations from cubic symmetry are minimal, as shown by the first example of an iron(II) M?ssbauer spectrum that exhibits no measurable quadrupole splitting. Two crystallographically distinct [Fe(OH2)6]2+ complexes are identified from inelastic neutron-scattering (INS) experiments conducted between 2 and 15 K. The data are modeled with the ligand-field Hamiltonian, H = lambdaL? + betaB(kL + 2?) + Delta(tet){Lz2 - (1/3)L(L + 1)} + Delta(rhom){Lx2 - Ly2}, operating in the ground-term (5)T(2g) (Oh) basis. An excellent reproduction of INS, M?ssbauer, HF-EPR, and magnetochemical data are obtained in the 2 and 15 K temperature regimes with the following parameters: lambda = -80 cm(-1); k = 0.8; site A Delta(tet) = 183 cm(-1), Delta(rhom)= 19 cm(-1); site B Delta(tet) = 181 cm(-1), Delta(rhom)= 12 cm(-1). The corresponding zero-field-splitting (ZFS) parameters of the conventional S = 2 spin Hamiltonian are as follows: site A D = 12.02 cm(-)(1), E = 2.123 cm(-1); site B D = 12.15 cm(-1), E = 1.37 cm(-1). A theoretical analysis of the variation of the energies of the low-lying states with respect to displacements along selected normal coordinates of the [Fe(OH2)6]2+, shows the zero-field splitting to be extremely sensitive to small structural perturbations of the complex. The expressions derived are discussed in the context of spin-Hamiltonian parameters reported for the [Fe(OH2)6]2+ cation in different crystalline environments.     

The electronic ground state of [V(urea)6]3+ probed by NIR luminescence, electronic Raman, and high-field EPR spectroscopies

The electronic structure of a trigonally distorted vanadium(III) complex, [V(urea)6](ClO4)3, and its deuterated analogue, [V(urea-d4)6](ClO4)3 has been investigated with Raman, luminescence, and high-frequency high-field electron paramagnetic resonance spectroscopies and with magnetic measurements. A broad electronic Raman transition is observed at around 1400 cm(-1) and attributed to a transition to the (3)E (D3) component of the (3)T1g (O(h)) ground state. The same splitting is seen in the near-infrared luminescence spectrum in the form of a similarly broad peak at 8450 cm(-1), 1400 cm(-1) lower in energy than the (1)E --> (3)A2 spin-flip transition. Powder high-frequency and high-field electron paramagnetic resonance spectra, magnetic susceptibilities, and magnetization studies give a precise measurement of the zero-field splitting and of the g values in this complex (D = 6.00(2) cm(-1), E = 0.573(6) cm(-1), g(x) = 1.848(2), g(y) = 1.832(4), and g(z) = 1.946(7)). A set of angular overlap model parameters is proposed that reproduces all spectroscopic observations, and an analysis of the influence of the bonding of urea on the trigonal distortion of the complex is given.     

A computationally fast variable importance test for random forests for high-dimensional data

Random forests are a commonly used tool for classification and for ranking candidate predictors based on the so-called variable importance measures. These measures attribute scores to the variables reflecting their importance. A drawback of variable importance measures is that there is no natural cutoff that can be used to discriminate between important and non-important variables. Several approaches, for example approaches based on hypothesis testing, were developed for addressing this problem. The existing testing approaches require the repeated computation of random forests. While for low-dimensional settings those approaches might be computationally tractable, for high-dimensional settings typically including thousands of candidate predictors, computing time is enormous. In this article a computationally fast heuristic variable importance test is proposed that is appropriate for high-dimensional data where many variables do not carry any information. The testing approach is based on a modified version of the permutation variable importance, which is inspired by cross-validation procedures. The new approach is tested and compared to the approach of Altmann and colleagues using simulation studies, which are based on real data from high-dimensional binary classification settings. The new approach controls the type I error and has at least comparable power at a substantially smaller computation time in the studies. Thus, it might be used as a computationally fast alternative to existing procedures for high-dimensional data settings where many variables do not carry any information. The new approach is implemented in the R package vita.     

The production and properties of polylactide composites filled with expanded graphite

Composites have been produced by melt-blending biodegradable polylactide (PLA) with commercially available expanded graphite (EG). Using different techniques of addition, the manifold effects of EG on PLA molecular, thermo-mechanical and fire-retardant properties were evaluated. The EG nanofiller provides PLA composites with competitive functional properties. They have a high rigidity, with Young's modulus and storage modulus increasing with EG content. They also have excellent thermal stability while preserving the glass transition and melting temperature of the original PLA matrix. Purification and pre-dispersion of EG nanofiller proved beneficial for preserving PLA molecular weights and led to improved mechanical performance. The presence of dispersed graphene nanolayers in PLA significantly accelerated the polyester crystallization process. The flame retardant properties also displayed improvements with a large decrease in the maximum rate of heat release as recorded by cone calorimetry, whereas the horizontal burning test (UL94 HB) was successfully passed revealing non-dripping and char formation.