Simultaneous temperature and 2D velocity measurements in a turbulent heated jet using combined laser-induced fluorescence and LDA

 This paper presents an efficient technique for the characterization of thermal transport properties in turbulent flows. The method is based on the temperature dependence of fluorescence, induced by laser radiation, of an organic dye. The laser-induced fluorescence technique is combined with 2D laser Doppler anemometry, in order to measure in the same sample volume simultaneously and instantaneously the temperature and velocity. The technique is demonstrated on a turbulent heated round jet: the mean and fluctuating dynamic and thermal fields are investigated, and the temperature-velocity cross-correlations are determined in order to characterize the turbulent diffusivity and the turbulent Prandtl number. Received: 30 October 1997/Accepted: 14 July 1998     

Tris­[(R)‐lact­amide‐κ2O,O′]­zinc(II) tetra­bromo­zincate

The title compound, tris­[(R)‐2‐hydroxy­propan­amide‐κ²O,O′]­zinc(II) tetra­bromo­zincate, [Zn(C₃H₇NO₂)₃][ZnBr₄], contains one monomeric six‐coordinate zinc complex cation and one tetrahedral [ZnBr₄]²⁻ anion. Both Zn^II atoms lie on threefold axes. Coordination in the cation occurs via the amide and hydroxy O atoms [Zn—O = 2.074 (5) and 2.073 (6) Å] and has a distorted octahedral geometry, with cis‐O—Zn—O angles in the range 76.2 (2)–109.2 (2)°. In the crystal structure, the cations and anions are linked by N—H⋯Br and O—H⋯O hydrogen bonds, generating a three‐dimensional network.     

Use of cw-CRDS for studying the atmospheric oxidation of acetic acid in a simulation chamber

The coupling between cavity ring-down spectroscopy (CRDS) and an environmental chamber in the investigation of photo-induced reaction mechanisms is demonstrated for the first time. The development of the CRDS device and the corresponding analytical performances are presented. The first application is devoted to the investigation of the branching ratio of the ^?OH radical reaction of CH₃C(O)OH and CH₃C(O)OD under tropospheric conditions. An environmental chamber coupled to two complementary detection systems is used:

gas chromatography with FTIR spectroscopy for quantitative detection of acetic acid;

CRDS for quantitative detection of CO₂.

Investigation of the reaction kinetics of ^?OH+CH₃C(O)OH gives a rate constant of (6.5±0.5)×10^-13 cm³?molecule^-1?s^-1 (296 K) and shows good agreement with literature data. The product study indicates that the H-abstraction channel from the acid group is the dominant pathway with a branching ratio of (78±13)%, whereas the corresponding D-abstraction channel in the ^?OH+CH₃C(O)OD reaction represents only (36±7)%. This result could be attributed to a strong kinetic isotope effect. Glyoxylic acid has also been detected for the first time as by-product. These results illustrate the high interest of the CRDS technique in the investigation of atmospheric relevant problems.     

Combined Infrared Multiphoton Dissociation with Ultraviolet Photodissociation for Ubiquitin Characterization

Herein we report the successful implementation of the consecutive and simultaneous photodissociation with high (213 nm) and low (10.6 μm) energy photons (HiLoPD, high-low photodissociation) on ubiquitin in a quadrupole-Orbitrap mass spectrometer. Absorption of high-energy UV photon is dispersed over the whole protein and stimulates extensive C–C_α backbone fragmentation, whereas low-energy IR photon gradually increases the internal energy and thus preferentially dissociates the most labile amide (C–N) bonds. We noticed that simultaneous irradiation of UV and IR lasers on intact ubiquitin in a single MS/MS experiment provides a rich and well-balanced fragmentation array of a/x, b/y, and z ions. Moreover, secondary fragmentation from a/x and z ions leads to the formation of satellite side-chain ions (d, v, and w) and can help to distinguish isomeric residues in a protein. Implementation of high-low photodissociation in a high-resolution mass spectrometer may offer considerable benefits to promote a comprehensive portrait of protein characterization.

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Graphical Abstract ?

     

Photodissociation pathways and lifetimes of protonated peptides and their dimers

Photodissociation lifetimes and fragment channels of gas-phase, protonated YA(n) (n = 1,2) peptides and their dimers were measured with 266 nm photons. The protonated monomers were found to have a fast dissociation channel with an exponential lifetime of ~200 ns while the protonated dimers show an additional slow dissociation component with a lifetime of ~2 μs. Laser power dependence measurements enabled us to ascribe the fast channel in the monomer and the slow channel in the dimer to a one-photon process, whereas the fast dimer channel is from a two-photon process. The slow (1 photon) dissociation channel in the dimer was found to result in cleavage of the H-bonds after energy transfer through these H-bonds. In general, the dissociation of these protonated peptides is non-prompt and the decay time was found to increase with the size of the peptides. Quantum RRKM calculations of the microcanonical rate constants also confirmed a statistical nature of the photodissociation processes in the dipeptide monomers and dimers. The classical RRKM expression gives a rate constant as an analytical function of the number of active vibrational modes in the system, estimated separately on the basis of the equipartition theorem. It demonstrates encouraging results in predicting fragmentation lifetimes of protonated peptides. Finally, we present the first experimental evidence for a photo-induced conversion of tyrosine-containing peptides into monocyclic aromatic hydrocarbon along with a formamide molecule both found in space.     

Copolymérisation du chlorure de vinyle et de carbonates de vinyle

Bulk copolymerizations of vinyl chloride (VC) and vinyl carbonate monomers were carried out at 50°. For vinyl-phenyl carbonate (CPV), the reactivity ratios are r_CV = 1.6 and r_CPV = 0.3. Slightly but regularly crosslinked copolymers are produced using moderate amount of bisvinylcarbonate; the crosslinking efficiency of the second vinyl function of the comonomer is very high, particularly if the two vinyl functions are linked through a flexible aliphatic moiety. Improved creep resistance is given by a small amount of crosslinking.     

Microwave spectrum of the hydroxyl radical in the ν= 1 Π3/2 state

The J = 7/2, 9/2, 11/2, 13/2 and 15/2 Λ doubling main lines of OH in the ν = 1, ² Π3/2 state have been measured. They are used with the UV and IR data to predict the low J frequencies with an accuracy sufficient for radioastronomical search.     

Decomposition Thermique du Dimanganese Decacarbonyle et du Dirhenium Decacarbonyle

The thermal behaviours of dimanganese decacarbonyl and dirhenium decacarbonyl were studied by TG, DTG and DTA. The decomposition products in different media were identified by X ray diffraction. In an inert medium, no important difference is observed between the two compounds. In an oxidizing medium, the identified products at 350? are a mixture of MnO andγ-Mn₂O₃ for the manganese compound and ReO₃ for that of Re. The decomposition temperatures of these metal carbonyls are functions of the studied medium. According to studies of metal-metal bond dissociation energies, Mn₂(CO)₁₀ is less stable than Re₂(CO)₁₀.