Modulating the photophysical properties of azamacrocyclic europium complexes with charge-transfer antenna chromophores

Two europium complexes with bis(bipyridine) azamacrocyclic ligands featuring pendant arms with or without π-conjugated donor groups are synthesized and fully characterized by theoretical calculations and NMR spectroscopy. Their photophysical properties, including two-photon absorption, are investigated in water and in various organic solvents. The nonfunctionalized ligand gives highly water-stable europium complexes featuring bright luminescence properties but poor two-photon absorption cross sections. On the other hand, the europium complex with an extended conjugated antenna ligand presents a two-photon absorption cross section of 45 GM at 720 nm but is poorly luminescent in water. A detailed solvent-dependent photophysical study indicates that this luminescence quenching is not due to the direct coordination of O-H vibrators to the metal center but to the increase of nonradiative processes in a protic solvent induced by an internal isomerization equilibrium.     

Determination of fireline intensity by oxygen consumption calorimetry

Fireline intensity is one of the most relevant quantities used in forest fire science. It helps to evaluate the effects of fuel treatment on fire behavior, to establish limits for prescribed burning. It is also used as a quantitative basis to support fire suppression activities. However, its measurement is particularly tricky for different reasons: difficulty in measuring the weight of the fuel consumed in the active fire front, difficulty to evaluate the rate of spread of the fire front, and uncertainty on combustion efficiency. In this study, an innovative and original approach to directly measure the fireline intensity at laboratory scale is proposed. Based on the oxygen consumption calorimetry principle, this methodology is applied here in case of spreading fires, for the first time. It allows for directly measuring the heat released by the fire front. The results are then used to test the famous Byram’s formulation that is generally applied to determine the fireline intensity. Combustion efficiency and effective heat of combustion results are provided. The uncertainty and the use of a full scale calorimeter instead of a bench scale calorimeter for this study are discussed.     

Quantitative and sensitive detection of rare mutations using droplet-based microfluidics

Somatic mutations within tumoral DNA can be used as highly specific biomarkers to distinguish cancer cells from their normal counterparts. These DNA biomarkers are potentially useful for the diagnosis, prognosis, treatment and follow-up of patients. In order to have the required sensitivity and specificity to detect rare tumoral DNA in stool, blood, lymph and other patient samples, a simple, sensitive and quantitative procedure to measure the ratio of mutant to wild-type genes is required. However, techniques such as dual probe TaqMan(?) assays and pyrosequencing, while quantitative, cannot detect less than ～1% mutant genes in a background of non-mutated DNA from normal cells. Here we describe a procedure allowing the highly sensitive detection of mutated DNA in a quantitative manner within complex mixtures of DNA. The method is based on using a droplet-based microfluidic system to perform digital PCR in millions of picolitre droplets. Genomic DNA (gDNA) is compartmentalized in droplets at a concentration of less than one genome equivalent per droplet together with two TaqMan(?) probes, one specific for the mutant and the other for the wild-type DNA, which generate green and red fluorescent signals, respectively. After thermocycling, the ratio of mutant to wild-type genes is determined by counting the ratio of green to red droplets. We demonstrate the accurate and sensitive quantification of mutated KRAS oncogene in gDNA. The technique enabled the determination of mutant allelic specific imbalance (MASI) in several cancer cell-lines and the precise quantification of a mutated KRAS gene in the presence of a 200,000-fold excess of unmutated KRAS genes. The sensitivity is only limited by the number of droplets analyzed. Furthermore, by one-to-one fusion of drops containing gDNA with any one of seven different types of droplets, each containing a TaqMan(?) probe specific for a different KRAS mutation, or wild-type KRAS, and an optical code, it was possible to screen the six common mutations in KRAS codon 12 in parallel in a single experiment.     

Contribution of heterogeneous strain field measurements and boundary conditions modelling in inverse identification of material parameters

The present paper aims at applying the Finite Element Updating inverse method to several sample geometries by the means of Digital Image Correlation. The full-field data are experimentally obtained from three geometries exhibiting increasing strain fields heterogeneities. For each test, a Finite Element model is built and boundary conditions are duplicated from the measured displacements at the sample borders. Field comparisons are performed at several time steps until fracture occurs and a Levenberg–Marquardt method is used to solve the optimization problem. Six parameters of an anisotropic elastic–plastic constitutive model are identified and validated through the simulation of a deep-drawing forming operation. Results show that identification quality is improved when heterogeneous strain fields are used.     

Numerical spectral analysis of a grid: Application to strain measurements

We present a nondestructive and noncontact extensometry technique, which has been developed in order to study the behavior of different materials such as polycarbonate, araldite, urethane, etc. A spectral analysis of a crossed grating marked on the surface of a specimen and recorded by a charge coupled device camera is presented. The procedure is based on the use of a bidimensional fast Fourier transform algorithm coupled with an interpolation process. It leads to the accurate determination of frequencies. Numerical simulations have been made to evaluate the strain sensitivity; it depends on both the initial phase and the number of cycles characterizing the grid. Theoretically, the strain sensitivity can reach 10^-5 in best cases, but practically it is notbetter than 10^-4. Several applications on different materials are presented: polyurethane, paper and cloth.     

Studies of an infinite element method for acoustical radiation

Infinite element computations are very efficient for predicting the vibro-acoustic response and sensitivities of a vibrating structure for an exterior acoustic domain. In addition, domain decomposition methods are very powerful algorithms for solving large linear systems in parallel. In this paper, an infinite element method is proposed and analyzed for parallel computations purpose. An original formulation of this method with Lagrange multipliers defined on (semi-)infinite space is presented. The implementation aspects of this method in an industrial acoustic software (SYSNOISE) are discussed. New numerical results illustrate the efficiency of the proposed method for realistic acoustical radiation problems.