Theoretical study of the OH-initiated atmospheric oxidation mechanism of perfluoro methyl vinyl ether, CF_3OCF=CF_2

Product formation in the reaction of perfluorinated methyl vinyl ether, CF_3OCF=CF_2, with OH radicals is studied theoretically using the M06-2X/aug-cc-pVTZ and CCSD(T) levels of theory. The stable end-products in an oxidative atmosphere are predicted to be perfluorinated methyl formate, CF_3OCFO, and fluorinated glycolaldehyde, CFOCF_2OH, both with CF_2O as coproduct. The prediction of glycolaldehyde as a product contrasts with experimental data, which found perfluoro glyoxal, CFOCFO, instead. The most likely explanation for this apparent disagreement is conversion of CFOCF_2OH to CFOCFO, e.g. by multiple catalytic agents present in the reaction mixture, wall reactions, and/or photolysis. The formation routes for the glyoxal product proposed in earlier work appear unlikely, and are not supported by theoretical or related experimental work

Health-related quality of life among children with Turner syndrome: controlled cross-sectional study

International audienceBACKGROUND : The aim of the study was to assess health-related quality of life (HR-QoL) in children with Turner syndrome in comparison with controls.METHODS : We prospectively recruited 16 female girls with Turner syndrome (mean age 15.2±2.6 years) and 78 female controls (mean age 12.7±2.8 years) in randomly selected schools. We used the PedsQL, a generic HR-QoL questionnaire (self and parents' versions).RESULTS : Global HR-QoL scores in Turner syndrome were lower than controls for self-reports (respectively, 74.3±3.0 vs. 82.8±1.3, p=0.01) and parents' reports (62.7±3.8 vs. 80.1±1.7, p<0.0001). In Turner syndrome, self-reported HR-QoL was impaired in school functioning (70.6±4.0 vs. 80.71±1.7, p=0.02), social functioning (78.2±4.0 vs. 90.4±1.8, p<0.01) and physical functioning (78.5±3.2 vs. 87.1±1.4, p=0.02), but not in emotional functioning. Parents' reported HR-QoL was impaired in all four dimensions.CONCLUSIONS : HR-QoL was impaired in this cohort of young females with Turner syndrome, as in previously reported adult studies. In addition to medical treatment and routine clinical follow-up, female girls and teenagers with Turner syndrome should also be supported psychologically by social, educational and psychotherapeutic interventions that aim to address their self-esteem and emotional difficulties

Temperature-(208-318 K) and pressure-(18-696Torr) dependent rate coefficients for the reaction between OH and HNO3

Abstract. Rate coefficients (k5) for the title reaction were ob- tained using pulsed laser photolytic generation of OH cou- pled to its detection by laser-induced fluorescence (PLP– LIF). More than 80 determinations of k5 were carried out in nitrogen or air bath gas at various temperatures and pres- sures. The accuracy of the rate coefficients obtained was en- hanced by in situ measurement of the concentrations of both HNO3 reactant and NO2 impurity. The rate coefficients show both temperature and pressure dependence with a rapid in- crease in k5 at low temperatures. The pressure dependence was weak at room temperature but increased significantly at low temperatures. The entire data set was combined with se- lected literature values of k5 and parameterised using a com- bination of pressure-dependent and -independent terms to give an expression that covers the relevant pressure and tem- perature range for the atmosphere. A global model, using the new parameterisation for k 5 rather than those presently ac- cepted, indicated small but significant latitude- and altitude- dependent changes in the HNO 3 / NO x ratio of between − 6 and + 6 %. Effective HNO 3 absorption cross sections (184.95 and 213.86 nm, units of cm 2 molecule − 1 ) were ob- tained as part of this work: σ 213 . 86 = 4.52 + 0 . 23 − 0 . 12 × 10 − 19 and σ 184 . 95 = 1.61 + 0 . 08 − 0 . 04 × 10 − 17

Combining Grid and Cloud Resources by Use of Middleware for SPMD Application

International audienceDistributed computing environments have evolved from in-house clusters to Grids and now Cloud platforms. We, as others, provide HPC benchmarks results over Amazon EC2 that show a lower performance of Cloud resources compared to private resources. So, it is not yet clear how much of impact Clouds will have in high performance computing (HPC). But hybrid Grid/Cloud computing may offer opportunities to increase overall applications performance, while benefiting from in-house computational resources extending them by Cloud ones only whenever needed. In this paper, we advocate the usage of ProActive, a well established middleware in the grid community, for mixed Grid/Cloud computing, extended with features to address Grid/Cloud issues with little or no effort for application developers. We also introduce a framework, developed in the context of the DiscoGrid project, based upon the ProActive middleware to couple HPC domain-decomposition SPMD applications in heterogeneous multi-domain environments. Performance results coupling Grid and Cloud resources for the execution of such kind of highly communicating and processing intensive applications have shown an overhead of about 15%, which is a non-negligible value, but lower enough to consider using such environments to achieve a better cost-performance trade-off than using exclusively Cloud resources

Characterization of two photon excited fragment spectroscopy (TPEFS) for HNO3 detection in gas-phase kinetic experiments

We have developed and tested two-photon excited fragment spectroscopy (TPEFS) for detecting HNO3 in pulsed laser photolysis kinetic experiments. Dispersed (220–330 nm) and time-dependent emission at (310 ± 5) nm following the 193 nm excitation of HNO3 in N2, air and He was recorded and analysed to characterise the OH(A2Σ) and NO(A2Σ+) electronic excited states involved. The limit of detection for HNO3 using TPEFS was ∼5 × 109 molecule cm−3 (at 60 torr N2 and 180 μs integration time). Detection of HNO3 using the emission at (310 ± 5 nm) was orders of magnitude more sensitive than detection of NO and NO2, especially in the presence of O2 which quenches NO(A2Σ+) more efficiently than OH(A2Σ). While H2O2 (and possibly HO2) could also be detected by 193 nm TPEFS, the relative sensitivity (compared to HNO3) was very low. The viability of real-time TPEFS detection of HNO3 using emission at (310 ± 5) nm was demonstrated by monitoring HNO3 formation in the reaction of OH + NO2 and deriving the rate coefficient, k2. The value of k2 obtained at 293 K and pressures of 50–200 torr is entirely consistent with that obtained by simultaneously measuring the OH decay and is in very good agreement with the most recent literature values

Current State of Java for HPC

About ten years after the Java Grande effort, this paper aims at providing a snapshot of the current status of Java for High Performance Computing. Multi-core chips are becoming mainstream, offering many ways for a Java Virtual Machine (JVM) to take advantage of such systems for critical tasks such as Just-In-Time compilation or Garbage Collection. We first perform some micro benchmarks for various JVMs, showing the overall good performance for basic arithmetic operations. Then we study a Java implementation of the Nas Parallel Benchmarks, using the ProActive middleware for distribution. Comparing this implementation with a Fortran/MPI one, we show that they have similar performance on computation intensive benchmarks, but still have scalability issues when performing intensive communications. Using experiments on clusters and multi-core machines, we show that the performance varies greatly, depending on the Java Virtual Machine used (version and vendor) and the kind of computation performed

HPC in Java: Experiences in Implementing the NAS Parallel Benchmarks

International audienceThis paper reports on the design, implementation and benchmarking of a Java version of the Nas Parallel Benchmarks. We first briefly describe the implementation and the performance pitfalls. We then compare the overall performance of the Fortran MPI (PGI) version with a Java implementation using the ProActive middleware for distribution. All Java experiments were conducted on virtual machines with different vendors and versions. We show that the performance varies with the type of computation but also with the Java Virtual Machine, no single one providing the best performance in all experiments. We also show that the performance of the Java version is close to the Fortran one on computational intensive benchmarks. However, on some communications intensive benchmarks, the Java version exhibits scalability issues, even when using a high performance socket implementation (JFS)

HPC in Java: Experiences in Implementing the NAS Parallel Benchmarks

International audienceThis paper reports on the design, implementation and benchmarking of a Java version of the Nas Parallel Benchmarks. We first briefly describe the implementation and the performance pitfalls. We then compare the overall performance of the Fortran MPI (PGI) version with a Java implementation using the ProActive middleware for distribution. All Java experiments were conducted on virtual machines with different vendors and versions. We show that the performance varies with the type of computation but also with the Java Virtual Machine, no single one providing the best performance in all experiments. We also show that the performance of the Java version is close to the Fortran one on computational intensive benchmarks. However, on some communications intensive benchmarks, the Java version exhibits scalability issues, even when using a high performance socket implementation (JFS)