Curiosities and counterexamples in smooth convex optimization

Mathematical Programming - Counterexamples to some old-standing optimization problems in the smooth convex coercive setting are provided. We show that block-coordinate, steepest descent with exact...     

High‐temperature kinetics of the reaction between CN and hydrocarbons using a novel high‐enthalpy flow tube

More than 70 molecules of varied nature have been identified in the envelopes of carbon‐rich stars through their spectral fingerprints in the microwave or far infrared regions. Many of them are carbon chain molecules and radicals, and a significant number are unique to the circumstellar medium. The determination of relevant laboratory kinetics data is critical to keep up with the development of the high spectral and spatial resolution observations and of the refinement of chemical models. Neutral–neutral reactions of the CN radical with unsaturated hydrocarbons could be a dominant route in the formation of cyanopolyynes, even at low temperatures and deserve a detailed laboratory investigation. The approach we have developed aims to bridge the temperature gap between resistively heated flow tubes and shock tubes. The present kinetic measurements are obtained using a new reactor combining a high‐enthalpy source with a flow tube and a pulsed laser photolysis–laser‐induced fluorescence system to probe the undergoing chemical reactions. The high‐enthalpy flow tube has been used to measure the rate constant of the reaction of the CN radical with propane (C₃H₈), propene (C₃H₆), allene (C₃H₄), 1,3‐butadiene (1,3‐C₄H₆), and 1‐butyne (C₄H₆) over a temperature range extending from 300 to 1200 K. All studied reactions of CN with unsaturated hydrocarbons are rapid, with rate coefficients greater than 10^?10 cm³ · molecule^?1 · s^?1 and exhibit slight negative temperature dependence above room temperature. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 753–766, 2012     

Some contributions with Petri nets for the modelling, analysis and control of HDS

Petri nets (PN) are useful for the modelling, analysis and control of hybrid dynamical systems (HDS) because PN combine in a comprehensive way discrete events and continuous behaviours. On one hand, PN are suitable for modelling the discrete part of HDS and for providing a discrete abstraction of continuous behaviours. On the other hand, continuous PN are suitable for modelling the continuous part of HDS and for working out a continuous approximation of the discrete part in order to avoid the complexity associated with the exponential growth of discrete states. This paper focuses on the advantages of PN as a modelling tool for HDS. Investigations of such models for diagnosis and control issues are detailed.

Taking inspiration from the discrete event approach, sensor selection for diagnosis is discussed according to the structural analysis of the PN models. Faults are represented with fault transitions and a faulty behaviour occurs when a sequence of transitions is fired that contains at least one fault transition. Minimal sets of observable places are defined for detecting and isolating faulty behaviours.

Taking inspiration from the continuous time approach, flow control of HDS modelled with continuous PN is also investigated. Gradient-based controllers are introduced in order to adapt the firing speeds of some controllable transitions according to a desired trajectory of the marking. The equilibria and stability of the controlled system are studied with Lyapunov functions.     

Overtone spectroscopy of H2D+ and D2H+ using laser induced reactions

The method of laser induced reaction is used to obtain high-resolution IR spectra of H2D+ and D2H+ in collision with n-H2 at a nominal temperature of 17 K. For this purpose three cw-laser systems have been coupled to a 22-pole ion trap apparatus, two commercial diode laser systems in the ranges of 6100-6600 cm(-1) and 6760-7300 cm(-1), respectively, and a high-power optical parametric oscillator tunable in the range of 2600-3200 cm(-1). In total, 27 new overtone and combination transitions have been detected for H2D+ and D2H+, as well as a weak line in the nu1 vibrational band of H2D+ (2(20)<--1(01)) at 3164.118 cm(-1). The line positions are compared to high accuracy ab initio calculations, showing small but mode-dependent differences, being largest for three vibrational quanta in the nu2 symmetric bending of H2D+. Within the experimental accuracy, the relative values of the ab initio predicted Einstein B coefficients are confirmed.     

Coordinatively unsaturated semisandwich complexes of ruthenium with phosphinoamine ligands and related species: a complex containing (R,R)-1,2-bis((diisopropylphosphino)amino)cyclohexane in a new coordination form kappa(3)P,P',N-eta(2)-P,N

The syntheses of the chloro complexes [Ru(eta5-C5R5)Cl(L)] (R = H, Me; L = phosphinoamine ligand) (1a-d) have been carried out by reaction of [(eta5-C5H5)RuCl(PPh3)2] or {(eta5-C5Me5)RuCl}4 with the corresponding phosphinoamine (R,R)-1,2-bis((diisopropylphosphino)amino)cyclohexane), R,R-dippach, or 1,2-bis(((diisopropylphosphino)amino)ethane), dippae. The chloride abstraction reactions from these compounds lead to different products depending on the starting chlorocomplex and the reaction conditions. Under argon atmosphere, chloride abstraction from [(eta5-C5Me5)RuCl(R,R-dippach)] with NaBAr'4 yields the compound [(eta5-C5Me5)Ru(kappa3P,P'-(R,R)-dippach)][BAr'4] (2b) which exhibits a three-membered ring Ru-N-P by a new coordination form of this phosphinoamine. However, under the same conditions the reaction starting from [(eta5-C5Me5)RuCl(dippae)] yields the unsaturated 16 electron complex [(eta5-C5Me5)Ru(dippae)][BAr'4] (2d). The bonding modes of R,R-dippach and dippae ligands have been analyzed by DFT calculations. The possibility of tridentate P,N,P-coordination of the phosphinoamide ligand to a fragment [(eta5-C5Me5)Ru]+ is always present, but only the presence of a cyclohexane unit in the ligand framework converts this bonding mode in a more favorable option than the usual P,P-coordination. Dinitrogen [(eta5-C5R5)Ru(N2)(L)][BAr'4] (3a-d) and dioxygen complexes [(eta5-C5H5)Ru(O2)(R,R-dippach)][BPh4] (4a) and [(eta5-C5Me5)Ru(O2)(L)][BPh4] (4b,d) have been prepared by chloride abstraction under dinitrogen or dioxygen atmosphere, respectively. The presence of 16 electron [(eta5-C5H5)Ru(R,R-dippach)]+ species in fluorobenzene solutions of the corresponding dinitrogen or dioxygen complexes in conjunction with the presence of [BAr'4]- gave in some cases a small fraction of [Ru(eta5-C5H5)(eta6-C6H5F)][BAr'4] (5a), which has been isolated and characterized by X-ray diffraction.     

A novel magnetic bead-based assay with high sensitivity and selectivity for analysis of telomerase in exfoliated cells from patients with bladder and colon cancer

Telomerase activity is elevated in more than 85% of cancer cells and absent in most of the normal cells and thus represents a potential cancer biomarker. We report its measurement in colon and bladder cancer cells captured using antibody-coated magnetic beads. The cells are lysed and telomerase activity is detected using a biosensor assay that employs an oligonucleotide containing the telomerase recognition sequence also covalently coupled to magnetic beads. Telomerase activity is measured by the incorporation of multiple biotinylated nucleotides at the 3'-end of the oligonucleotide strands during elongation which are then reacted with streptavidin-conjugated horseradish peroxidase. A luminescent signal is generated when hydrogen peroxidase is added in the presence of luminol and a signal enhancer. LOD experiments confirm sensitivity down to ten cancer cell equivalents. The telomerase assay reliably identified patient samples considered by an independent pathological review to contain cancer cells. Samples from normal healthy volunteers were all telomerase negative. The assay, which is amenable to automation, demonstrated high sensitivity and specificity in a small clinical cohort, making it of potential benefit as a first line assay for detection and monitoring of colon and bladder cancer.     

Use of multiple reaction monitoring for multiplex analysis of colorectal cancer-associated proteins in human feces

Colorectal cancer (CRC) is the second most common cause of cancer-related deaths worldwide with an annual incidence of almost a million cases and an annual mortality around 500,000. The fecal occult blood test is currently the first line method for CRC screening, but has unacceptably low sensitivity and specificity. Improved screening tests are therefore urgently required for early-stage CRC screening when therapy is most likely to be effective. We describe a discovery-based proteomics hypothesis using orthogonal multi-dimensional fractionation (1-D SDS-PAGE, RP-HPLC, size exclusion chromatography) to mine deep into the fecal proteome for the initial discovery process, which generated a library containing 108 human fecal proteins with the associated peptide and MS/MS data. These data were then used to develop and optimize a multiplex multiple reaction monitoring assay for 40 non-redundant human proteins present in the feces. To show proof of principal for clinical analysis, multiplex screening of these 40 proteins was carried out on fecal samples from eight CRC patient and seven normal volunteers. We identified 24 proteins consistently found in all samples and nine proteins found only in the CRC patients, showing the potential of this approach for the analysis of potential CRC biomarkers. Absolute quantitation using C-terminal isotopically labeled synthetic peptides corresponding to hemoglobin and carcinoembryonic antigen 5 was also performed.     

Strong-field molecular ionization: determination of ionization probabilities calibrated with field-free alignment

We report an original optical method providing the probability of molecular ionization induced by femtosecond laser pulses. The approach consists of exploiting molecular alignment to extract reliable information about ionization. The cross defocusing technique implemented for this purpose reveals a sensitivity with respect to postpulse alignment, as well as to the free electron density induced by the ultrashort laser pulse. The analysis of the resulting signal thus gives access to absolute single-ionization probabilities calibrated through the degree of alignment, provided that free electrons are produced mainly by single ionization. The relevance of the method is assessed in N2.