Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956     

Five Novel Taccalonolides from the Roots of the Vietnamese Plant Tacca paxiana

Chemical investigation of the roots of the Vietnamese plant Tacca paxiana resulted in the isolation of five new steroidal compounds, taccalonolide R ( 6 ), S ( 7 ), T ( 8 ), U ( 9 ), and V ( 10 ). Their structures were established on the basis of NMR and mass‐spectral data. In addition, the five known taccalonolides A ( 1 ), B ( 2 ), E ( 3 ), K ( 4 ), and N ( 5 ) were also isolated and identified.     

Stability radii of positive linear Volterra-Stieltjes equations

We study stability radii of linear Volterra-Stieltjes equations under multi-perturbations and affine perturbations. A lower and upper bound for the complex stability radius with respect to multi-perturbations are given. Furthermore, in some special cases concerning the structure matrices, the complex stability radius can precisely be computed via the associated transfer functions. Then, the class of positive linear Volterra-Stieltjes equations is studied in detail. It is shown that for this class, complex, real and positive stability radius under multi-perturbations or multi-affine perturbations coincide and can be computed by simple formulae expressed in terms of the system matrices. As direct consequences of the obtained results, we get some results on robust stability of positive linear integro-differential equations and of positive linear functional differential equations. To the best of our knowledge, most of the results of this paper are new.     

Effect of solvent nature on spin exchange in rigid nitroxide biradicals

Intramolecular electron spin exchange as a function of temperature and solvent viscosity and polarity has been studied by X-band electron paramagnetic resonance (EPR) spectroscopy in two rigid nitroxide biradicals existing in one spatial conformation only. Temperature variations of the isotropic hyperfine splitting constanta and exchange integral value |J/a| were measured from EPR spectra and subsequently analyzed. The interaction of polar solvent molecules with >N-O fragments of nitroxide groups led to a slight decrease of the |J/a| value with the increase of temperatureT. In contrast, the interaction of polar solvent molecules with functional groups inside the bridge resulted in a noticeable increase of |J/a| vs.T. In the last case, a coverse relationship between the values of |J/a| and the hyperfine splitting constanta has been observed for solvents with different polarity.     

Effects of physical aging on yielding kinetics of polycarbonate

The purpose of this work was to investigate the effects of physical aging on the kinetics of yielding in polycarbonate. PC samples were annealed over a wide range of aging times and temperatures. Both tensile and compressive tests were performed over various loading rates and temperatures to analyze the effects of aging time and aging temperature on yielding kinetics. Two grades of polycarbonate, Makrolon, of different molecular weights, PC-2608 (low M_w), and PC-3208 (high M_w), supplied by Bayer were analyzed. In unaged condition, PC is hard and tough, but after aging, it becomes more brittle. In terms of molecular movement, the yielding process is a thermally activated process involving inter- and intra-molecular motions. The time–temperature dependence of yielding behavior can be separated into two regions. Aging does not affect localized molecular motions of the β process during yielding. Physical aging in PC results in a slower jump rate of the main segments of macromolecules between two equilibrium positions. It reduces the flexibility of the macromolecules and thus, makes the polymer more brittle. Heat aging also causes a decrease of the entropy (ΔS) in polycarbonate, and this decrease is more important when the molecular weight is reduced. Increasing the annealing time and temperature results in a continuous reduction of ΔS. The rate of aging decreases with decreasing annealing temperature and below about 30 °C, no aging takes place. Annealing also strongly affects the excess of enthalpy in PC. However the effect of physical aging on yielding differs to that on enthalpy excess. The kinetics of yielding and aging processes in polycarbonate are also different. An increase in the strain rate does not have the same effect on the yield stress as an increase in the aging time by a same factor.     

Infine Functions, Nonsmooth Alternative Theorems and Vector Optimization Problems

In this paper we introduce a new notion of infine nonsmooth functions and give several characterizations of infineness property. We prove alternative theorems with mixed constraints (i.e., inequality and equality constraints) being described by invex-infine nonsmooth functions. We establish a necessary and sufficient condition for a solution of a vector optimization problem involving mixed constraints to be a properly efficient solution.     

Some New Results on Key Distribution Patterns and Broadcast Encryption

This paper concerns methods by which a trusted authority can distribute keys and/or broadcast a message over a network, so that each member of a privileged subset of users can compute a specified key or decrypt the broadcast message. Moreover, this is done in such a way that no coalition is able to recover any information on a key or broadcast message they are not supposed to know. The problems are studied using the tools of information theory, so the security provided is unconditional (i.e., not based on any computational assumption).In a recent paper st95a, Stinson described a method of constructing key predistribution schemes by combining Mitchell-Piper key distribution patterns with resilient functions; and also presented a construction method for broadcast encryption schemes that combines Fiat-Naor key predistribution schemes with ideal secret sharing schemes. In this paper, we further pursue these two themes, providing several nice applications of these techniques by using combinatorial structures such as orthogonal arrays, perpendicular arrays, Steiner systems and universal hash families.     

Reactions de photoaddition de benzo[b]selenophenes avec l'acetylene dicarboxylate de methyle et avec le dichloro-1,2 ethylene

Photoirradiated in presence of acetophenone, benzo[b]selenophene and its 3-methyl derivative add to dimethyl acetylenedicarboxylate. In each ease, the primary reaction product is unstable and has not been isolated. Photoexeited in its triplet state (the energy of which is in the neighbourhood of 69 $\text{kcal}\text{mole}$) benzo[b]selenophene and its 2- and 3-methyl, 2,3 dimethyl, 3 acetoxy and 2-methyl-3-acetoxy derivatives add to 1,2 dichloroethylene leading to cyclobutanes. Neither cyclo-addition occurs in absence of photosensitiser. Single-crystal X-ray analysis gave the structures of the two adducts of 3-acetoxybenzo[b]selenophene with trans-1,2-dichloroethylene. In both compounds the chlorine atoms are trans.     

3-(Triethoxysilyl)propionitrile sol-gel coating

3-(Triethoxysilyl)propionitrile (TESPN) sol-gel has been prepared under different conditions. It was employed for coating the surfaces of quartz and aluminum. Infrared (IR) and Raman spectra of TESPN and TESPN sol-gels have been recorded in the study of the sol-gel process. Transmission and reflection absorption IR (RAIR) spectra of TESPN sol-gel coated quartz and aluminum have also been collected for better understanding the film formation on the substrate surfaces. Spectra collected at different temperatures indicated that the silane film on quartz decomposes at 700 degrees C. Results from thermal gravimetric analysis (TGA) supported this result. Based on the group frequencies and the spectral behavior in different states, some vibrational modes were assigned to the observed bands. The anticorrosion behavior of the sol-gel coated aluminum in comparison with the uncoated metal was evaluated by measuring the potentiodynamic polarization and electrochemical impedance spectra (EIS).