Viscoelastic phase diagram of fluorinated and grafted polymer films and proton‐exchange membranes for fuel cell applications

The influence of temperature and moisture activity on the viscoelastic behavior of fluorinated membranes for fuel cell applications was investigated. Uncrosslinked and crosslinked ethylene tetrafluoroethylene (ETFE)‐based proton‐conducting membranes were prepared by radiation grafting and subsequent sulfonation and their behavior was compared with ETFE base film and commercial Nafion^® NR212 membrane. Uniaxial tensile tests and stress relaxation tests at controlled temperature and relative humidity (RH) were carried out at 30 and 50 °C for 10% < RH < 90%. Grafted films were stiffer and exhibited stronger strain hardening when compared with ETFE. Similarly, both uncrosslinked and crosslinked membranes were stiffer and stronger than Nafion^®. Yield stress was found to decrease and moisture sensitivity to increase on sulfonation. The viscoelastic relaxation of the grafted films was found to obey a power‐law behavior with exponent equal to ?0.04 ± 0.01, a factor of almost 2 lower than ETFE, weakly influenced by moisture and temperature. Moreover, the grafted films presented a higher hygrothermal stability when compared with their membranes counterparts. In the case of membranes, a power‐law behavior at RH < 60% was also observed. However, a markedly different behavior was evident at RH > 60%, with an almost single relaxation time exponential. An exponential decrease of relaxation time with RH from 60 s to 10 s was obtained at RH ≥ 70% and 30 °C. The general behavior of grafted films observed at 30 °C was also obtained at 50 °C. However, an anomalous result was noticed for the membranes, with a higher modulus at 50 °C when compared with 30 °C. This behavior was explained by solvation of the sulfonic acid groups by water absorption creating hydrogen bonding within the clusters. A viscoelastic phase diagram was elaborated to map critical conditions (temperature and RH) for transitions in time‐dependent behavior, from power‐law scaling to exponential scaling. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1139–1148     

Lung Cancer Detection by Native Fluorescence Spectra of Body Fluids—A Preliminary Study

Lung cancer takes a heavy toll every year, since the survival rate is not more than 15%. In this paper, we present results of a novel technique based on the autofluorescence of body fluids like blood plasma, acetone extract of cellular components, sputa and urine of lung cancer patients (N = 27). A set of ratio parameters based on the fluorescence peaks of tryptophan and elastin, in plasma and sputum; flavin, NADH (reduced nicotinamide adenine dinucleotide) and porphyrin in urine; porphyrin alone in acetone extract of formed elements, were all evaluated. Similar sets of ratios were obtained for age adjusted normal controls (N = 27) and all these ratios were given as inputs to multivariate (principle component and discriminant) analyses, which showed that the two groups could be classified with an accuracy of about 90%. Since the instrumentation involved was an ordinary steady state Xe lamp based spectrofluorometer, the technique is of significant advantage in screening and early detection of lung cancer in high risk population such as heavy smokers.     

Solving a robotic assembly line balancing problem using efficient hybrid methods

In this paper we are studying a robotic assembly line balancing problem. The goal is to maximize the efficiency of the line and to balance the different tasks between the robots by defining the suitable tasks and components to assign to each robot. We are interested in a robotic line which consists of seizing the products on a moving conveyor and placing them on different location points. The performances evaluations of the system are done using a discret event simulation model. This latter has been developed with C++ language. As in our industrial application we are bounded by the execution time, we propose some resolution methods which define the suitable component and point positions in order to define the strategy of pick and place for each robot. These methods are based on the ant colony optimization, particle swarm optimization and genetic algorithms. To enhance the quality of the developed algorithms and to avoid local optima, we have coupled these algorithms with guided local search. After that, an exact method based on full enumeration is also developed to assess the quality of the developed methods. Then, we try to select the best algorithm which is able to get the best solutions with a small execution time. This is the main advantage of our methods compared to exact methods. This fact represents a great interest taking in consideration that the selected methods are used to manage the functioning of real industrial robotic assembly lines. Numerical results show that the selected algorithm performs optimally for the tested instances in a reasonable computation time and satisfies the industrial constraint.     

Low-temperature H2 sensing in self-assembled organotin thin films

Self-assembled nanoporous tin-based hybrid thin films prepared by the sol-gel method from organically-bridged ditin hexaalkynides detect hydrogen gas from 50 to 200 °C at the 200-10,000 ppm level. This finding opens a fully new class of gas-sensing materials as well as a new opportunity to integrate organic functionality in gas sensing metal oxides.     

Helichrysum gymnocephalum essential oil: chemical composition and cytotoxic, antimalarial and antioxidant activities, attribution of the activity origin by correlations

Helichrysum gymnocephalum essential oil (EO) was prepared by hydrodistillation of its leaves and characterized by GC-MS and quantified by GC-FID. Twenty three compounds were identified. 1,8-Cineole (47.4%), bicyclosesquiphellandrene (5.6%), γ-curcumene (5.6%), α-amorphene (5.1%) and bicyclogermacrene (5%) were the main components. Our results confirmed the important chemical variability of H. gymnocephalum. The essential oil was tested in vitro for cytotoxic (on human breast cancer cells MCF-7), antimalarial (Plasmodium falciparum: FcB1-Columbia strain, chloroquine-resistant) and antioxidant (ABTS and DPPH assays) activities. H. gymnocephalum EO was found to be active against MCF-7 cells, with an IC(50) of 16 ± 2 mg/L. The essential oil was active against P. falciparum (IC(50) = 25 ± 1 mg/L). However, the essential oil exhibited a poor antioxidant activity in the DPPH (IC(50) value > 1,000 mg/L) and ABTS (IC(50) value = 1,487.67 ± 47.70 mg/L) assays. We have reviewed the existing results on the anticancer activity of essential oils on MCF-7 cell line and on their antiplasmodial activity against the P. falciparum. The aim was to establish correlations between the identified compounds and their biological activities (antiplasmodial and anticancer). β-Selinene (R2 = 0.76), α-terpinolene (R2 = 0.88) and aromadendrene (R2 = 0.90) presented a higher relationship with the anti-cancer activity. However, only calamenene (R2 = 0.70) showed a significant correlation for the antiplasmodial activity.     

Quasistatic frictional thermo‐piezoelectric contact problem

We consider here a mathematical model describing the bilateral frictional contact between a thermo‐piezoelectric body and a thermally conductive foundation. We model the behavior of the material with a linear thermo‐electro‐elastic constitutive law. The process is assumed to be quasistatic and the contact is modeled with a nonlocal version of Coulomb's dry friction law, in which the frictional heat generated in the process, is taken into account. We drive a variational formulation of the problem and establish the existence of its weak solution.     

Gas-phase thermolysis of benzotriazole derivatives. Part 3: Kinetic and mechanistic evidence for biradical intermediates in pyrolysis of aroylbenzotriazoles and related compounds

Gas-phase pyrolysis (static and FVP) of 1-aroylbenzotriazoles gave the corresponding substituted benzoxazole, benzimidazole, benzamide, N-phenylbenzamide, phenanthridin-6(5H)-one derivatives and 1-cyanocyclopentadiene. The present kinetic and mechanistic findings also provide further evidence of the involvement of biradical or carbene reactive intermediates in the reaction pathway of gas-phase pyrolysis of benzotriazoles.     

Isomorphismes bicroissants des cônes convexes

Sans résumé     

A doubly folded spacer in a self-assembled hybrid material

The hydrolysis of a bridged alpha,omega-bis(trialkynylstannylated) compound leads to a hybrid material ordered by self-assembly where the spacer forms two six-membered [1,2]oxastanninane rings by intramolecular coordination.     

Entropy solutions of anisotropic elliptic nonlinear obstacle problem with measure data

We prove the existence of an entropy solution for a class of nonlinear anisotropic elliptic unilateral problem associated to the following equation $$\begin{aligned} -\sum _{i=1}^{N} \partial _i a_i(x,u, \nabla u) -\sum _{i=1}^{N}\partial _{i}\phi _{i}( u)=\mu , \end{aligned}$$where the right hand side $$\mu $$ belongs to $$L^{1}(\Omega )+ W^{-1, \vec {p'}}(\Omega )$$. The operator $$-\sum _{i=1}^{N} \partial _i a_i(x,u, \nabla u) $$ is a Leray–Lions anisotropic operator and $$\phi _{i} \in C^{0}({\mathbb {R}}, {\mathbb {R}})$$.