Dynamic shear and compressional behavior of polydimethylsiloxanes: Ultrasonic and low frequency characterization

The dynamic rheological properties of a series of entangled polydimethylsiloxanes are investigated. Rheometrical shear measurements are first reported for three different molecular weight samples, together with ultrasonic tests, thus allowing to obtain dynamic shear master curves over ten decades. Winter‘s model for slightly polydisperse polymers is used and works well in this case. This provides an example of the applicability of this model. The propagation of longitudinal waves in the MHz range for the same PDMSs is studied next. The results are analyzed and combined with static measurements of the compressibility. They indicate that different relaxation mechanisms have to be considered in shear and compression, and that the ratio between volume and shear viscosity is frequency dependent, with a preponderance for shear effects at higher frequencies. Shear and compressional relaxational mechanisms are also well separated. Moreover, it is verified that the shear and compressional moduli are independent of the molecular weight in the transition region, above a certain frequency. This frequency corresponds to a wavelength comparable to the distance between entanglements, in the case of shear waves. Received: 9 December 1997 Accepted: 30 March 1998     

Advantages of the scheduled selected reaction monitoring algorithm in liquid chromatography/electrospray ionization tandem mass spectrometry multi‐residue analysis of 242 pesticides: a comparative approach with classical selected reaction monitoring mode

This paper illustrates the advantages of using the scheduled selected reaction monitoring (sSRM) algorithm available in Analyst® Software 1.5 to build SRM acquisition methods in the application field of pesticide multi‐residue analysis. The principle is to monitor the SRM transitions only when necessary. Based on the analytes' retention times, the scheduled SRM algorithm decreases the number of concurrent SRM transitions monitored at any point in time, allowing both cycle time and dwell time to remain optimal at higher levels of SRM multiplexing. To compare the scheduled SRM and the classical SRM modes, a mixture containing 242 multi‐class pesticides has been analyzed ten times by three acquisition methods, using liquid chromatography/tandem mass spectrometry (LC/MS/MS) with an API 4000 QTrap? mass spectrometer. The scheduled SRM mode demonstrates better results in all fields: more data points per peak, better reproducibility (coefficients of variation (CVs) <5%) and higher signal‐to‐noise ratio (S/N), even when the number of SRM transitions is doubled. The use of scheduled SRM mode instead of the classical one gives an enhancement of the limits of quantification by a factor two or even higher (up to six), depending on the analyte transitions. Copyright © 2010 John Wiley & Sons, Ltd.     

Control of a separated boundary layer: reduced-order modeling using global modes revisited

The possibility of model reduction using global modes is readdressed, aiming at the controlling of a globally unstable separation bubble induced by a bump geometry. A combined oblique and orthogonal projection approach is proposed to design an estimator and controller in a Riccati-type feedback setting. An input?Coutput criterion is used to appropriately select the modes of the projection basis. The full-state linear instability dynamics is shown to be successfully controlled by the feedback coupling with controllers of moderate degrees of freedom.     

K-Theory of the Indicial Algebra of a Manifold with Corners

We compute the K-theory, groups of the C ^*-algebra of the groupoid of a manifold with corners, in which the analytic index takes its values.     

Effet dispersif de la loi d'Exner menant à l'équation de Benjamin–Ono : ondulations d'un sol meubleExner's law dispersive effects leading to Benjamin–Ono equation: waves over an erodible bed

The flow over an erodible bed is revisited supposing that the flux of sediments is proportional to the slip velocity of the potential flow. This gives a linear Benjamin–Ono equation which is numerically solved, this solution is favorably compared to a selfsimilar approached solution. To cite this article: P.-Y. Lagrée et al., C. R. Mecanique 331 (2003).     

Probing of porphyrin surface chemistry in systems with laser-ablated Ag nanoparticle hydrosol: role of thiosulfate anions

The influence of sodium thiosulfate (THS) concentration in Ag colloid/THS/H(2)TMPyP and Ag colloid/H2TMPyP/THS systems (H2TMPyP = 5,10,15,20-tetrakis(1-methyl-4-pyridyl)porphyrin) was investigated by a combination of surface-enhanced resonance Raman scattering (SERRS) spectroscopy, surface plasmon extinction (SPE) measurements, and transmission electron microscopy (TEM). THS was found to have a strong impact on Ag nanoparticle surface structure and aggregation state and on interaction with H2TMPyP probe molecules, as evidenced by variations of the SERRS spectrum. In the Ag colloid/THS/H2TMPyP system, when laser-ablated Ag colloid was THS pretreated prior to the porphyrin addition, a critical threshold THS concentration (4 x 10(-5) M) was discovered. At concentrations below the threshold, THS mainly reduces the number of Ag+ adsorption sites. This leads to increased Ag nanoparticle aggregation prior to the porphyrin addition and significant weakening of the overall SERRS signal. Dominant contributions in the SERRS spectrum correspond to free base H2TMPyP and Ag+ containing the AgTMPyP form. At concentrations above the threshold, THS mediates also the formation and stabilization of new adsorption sites, probably Ag(0) sites. This induces a turn in the aggregation state of the pretreated Ag-c/THS system, an increase of the overall SERRS signal, and the appearance of a new spectral form of Ag metalated porphyrin.     

Variable-Temperature and Variable-Pressure Kinetic and Equilibrium studies of formation and dissociation of [V(H2O)5NCS]2+

The kinetics of formation and dissociation of [V(H₂O)₅NCS]²⁺ have been studied, as a function of excess metal-ion concentration, temperature, and pressure, by the stopped-flow technique. The thermodynamic stability of the complex was also determined spectrophotometrically. The kinetic and equilibrium data were submitted to a combined analysis. The rate constants and activation parameters for the formation (f) and dissociation (r) of the complex are: k/M ^?1 · S^?1 = 126.4, k/s^?1 = 0.82; ΔH /kJ · mol^?1 = 49.1, ΔH/kJ · mol^?1 = 60.6; ΔS/ J·K^?1·mol^?1= ?39.8, ΔSJ·K^?1·mol^?1 = ?43.4; ΔV/cm³·mol^?1 = ?9.4, and ΔV/cm³ · mol^?1 =?17.9. The equilibrium constant for the formation of the monoisothiocynato complex is K²⁹⁸/M ^?1 = 152.9, and the enthalpy and entropy of reaction are ΔH⁰/kJ · mol^?1 = ? 11.4 and ΔS⁰/J. K^?1mol^?1 = +3.6. The reaction volume is ΔV⁰/cm³· mol^?1 = +8.5. The activation parameters for the complex-formation step are similar to those for the water exchange on [V(H₂O)₆]³⁺ obtained previously by NMR techniques. The activation volumes for the two processes are consistent with an associative interchange, I_a, mechanism.     

Connecting terminal carboxylate groups in nine-coordinate lanthanide podates: consequences on the thermodynamic,structural, electronic,and photophysical properties

The hydrolysis of terminal (t)butyl-ester groups provides the novel nonadentate podand tris[2-[N-methylcarbamoyl-(6-carboxypyridine-2)-ethyl]amine] (L13) which exists as a mixture of slowly interconverting conformers in solution. At pH = 8.0 in water, its deprotonated form [L13 - 3H](3-) reacts with Ln(ClO(4))(3) to give the poorly soluble and stable podates [Ln(L13 - 3H)] (log(beta(110)) = 6.7-7.0, Ln = La-Lu). The isolated complexes [Ln(L13 - 3H)](H(2)O)(7) (Ln = Eu, 8; Tb, 9; Lu, 10) are isostructural, and their crystal structures show Ln(III) to be nine-coordinate in a pseudotricapped trigonal prismatic site defined by the donor atoms of the three helically wrapped tridentate binding units of L13. The Ln-O(carboxamide) bonds are only marginally longer than the Ln-O(carboxylate) bonds in [Ln(L13 - 3H)], thus producing a regular triple helix around Ln(III) which reverses its screw direction within the covalent Me-TREN tripod. High-resolution emission spectroscopy demonstrates that (i) the replacement of terminal carboxamides with carboxylates induces only minor electronic changes for the metallic site, (ii) the solid-state structure is maintained in water, and (iii) the metal in the podate is efficiently protected from interactions with solvent molecules. The absolute quantum yields obtained for [Eu(L13 - 3H)] (Phi(Eu)(tot)= 1.8 x 10(-3)) and [Tb(L13 - 3H)] (Phi(Eu)(tot)= 8.9 x 10(-3)) in water remain modest and strongly contrast with that obtained for the lanthanide luminescence step (Phi(Eu) = 0.28). Detailed photophysical studies assign this discrepancy to the small energy gap between the ligand-centered singlet ((1)pi pi*) and triplet ((3)pi pi*) states which limits the efficiency of the intersystem crossing process. Theoretical TDDFT calculations suggest that the connection of a carboxylate group to the central pyridine ring prevents the sizable stabilization of the triplet state required for an efficient sensitization process. The thermodynamic and electronic origins of the advantages (stability, lanthanide quantum yield) and drawbacks (solubility, sensitization) brought by the "carboxylate effect" in lanthanide complexes are evaluated for programming predetermined properties in functional devices.     

Measurement of the fundamental thermal noise limit in a cryogenic sapphire frequency standard using bimodal maser oscillations

We report observations of the Schawlow-Townes noise limit in a cryogenic sapphire secondary frequency standard. The effect causes a fundamental limit to the frequency stability, and was measured through the novel excitation of a bimodal maser oscillation of a Whispering Gallery doublet at 12.04 GHz. The beat frequency of 10 kHz between the oscillations enabled a sensitive probe for this measurement of fractional frequency instability of 10(-14) tau(-1/2) with only 0.5 pW of output power.