Space correlation measurements in a forced shear layer with wall injection

Comprehension of wall-injection flow in a channel in the presence of different geometric discontinuities is necessary as part of the general investigations concerning combustion instabilities of solid propellant rocket motors. In order to characterise the aerodynamic flow field and to evaluate the influence of an obstacle inside a porous channel in such a case, experimental studies were conducted on a 1/40 scale model of the new ARIANE V motor. In fact, the flow is only induced by wall-injection and the presence of an obstacle creates a particular shear layer development in the obstacle wake. Particular attention was given to the unstable dynamic conditions of the shear layer. A thermal seeding of the shear layer was made in order to qualify the heat transfer therein, and especially to emphasise the turbulent structure development. Transverse and longitudinal spatial correlations were measured to characterise turbulence scales in the shear layer. At the origin of the shear layer, the decay of turbulence memory is found to be similar to that observed in a forced flow boundary layer, but the injecting wall modifies the change in structures. The wall flow is found to preserve the turbulent structures in such a way that the turbulence memory predominates in a longitudinal direction.List of Symbols f frequency (Hz) - h channel height (m) - h _v obstacle height (m) - L mean dimension of large structures (m) - P pressure (Pa) - m mass flow rate (kg/s) - r distance between probes in X direction (m) - r ^+(–) distance between probes in Y direction (m) - u longitudinal velocity in X direction (m/s) - v transversal velocity in Y direction (m/s) - T temperature (K) - x,y,z axis system (m) - t = T-T _amb (K) - v kinematic viscosity (mVs) - density (kg/m³) - characteristic porous size (urn) - _u longitudinal rms (m/s) - I _u dynamic turbulence intensity _u /u _max - I _T thermal turbulence intensity - M Mach number u/a - Re _w wall Reynolds number v _w h/v - Re _c longitudinal Reynolds number u _c h/v - R _uT thermal dynamic correlation coefficient - St Strouhal number fh/u - X,Y,Z axis system normalised by the channel height h - X _S longitudinal position of the obstacle - X X-X _S - amb ambient reference - c flowing cavity - fav head end - l lateral direction - g longitudinal direction max maximum at a longitudinal position - w wall The authors thank the CNES for its financial support, and in particular E. Robert and R. Bee.     

Fourier transform spectroscopy around 3 μm with a broad difference frequency comb

We characterize a new mid-infrared frequency comb generator based on difference frequency generation around 3.1 μm. High power per comb mode (>10^?7 W/mode) is obtained over a broad spectral span (>750 nm, >790 cm^?1). The source is used for direct absorption spectroscopy with a Michelson-based Fourier transform interferometer.     

Chemical alterations to murine brain tissue induced by formalin fixation: implications for biospectroscopic imaging and mapping studies of disease pathogenesis

Understanding biochemical mechanisms and changes associated with disease conditions and, therefore, development of improved clinical treatments, is relying increasingly on various biochemical mapping and imaging techniques on tissue sections. However, it is essential to be able to ascertain whether the sampling used provides the full biochemical information relevant to the disease and is free from artefacts. A multi-modal micro-spectroscopic approach, including FTIR imaging and PIXE elemental mapping, has been used to study the molecular and elemental profile within cryofixed and formalin-fixed murine brain tissue sections. The results provide strong evidence that amino acids, carbohydrates, lipids, phosphates, proteins and ions, such as Cl(-) and K(+), leach from tissue sections into the aqueous fixative medium during formalin fixation of the sections. Large changes in the concentrations and distributions of most of these components are also observed by washing in PBS even for short periods. The most likely source of the chemical species lost during fixation is the extra-cellular and intra-cellular fluid of tissues. The results highlight that, at best, analysis of formalin-fixed tissues gives only part of the complete biochemical "picture" of a tissue sample. Further, this investigation has highlighted that significant lipid peroxidation/oxidation may occur during formalin fixation and that the use of standard histological fixation reagents can result in significant and differential metal contamination of different regions of tissue sections. While a consistent and reproducible fixation method may be suitable for diagnostic purposes, the findings of this study strongly question the use of formalin fixation prior to spectroscopic studies of the molecular and elemental composition of biological samples, if the primary purpose is mechanistic studies of disease pathogenesis.     

Biotransformations of Anticancer Ruthenium(III) Complexes: An X‐Ray Absorption Spectroscopic Study

An anti‐metastatic drug, NAMI‐A ((ImH)[Ru^IIICl₄(Im)(dmso)]; Im=imidazole, dmso=S‐bound dimethylsulfoxide), and a cytotoxic drug, KP1019 ((IndH)[Ru^IIICl₄(Ind)₂]; Ind=indazole), are two Ru‐based anticancer drugs in human clinical trials. Their reactivities under biologically relevant conditions, including aqueous buffers, protein solutions or gels (e.g, albumin, transferrin and collagen), undiluted blood serum, cell‐culture medium and human liver (HepG2) cancer cells, were studied by Ru K‐edge X‐ray absorption spectroscopy (XAS). These XAS data were fitted from linear combinations of spectra of well‐characterised Ru compounds. The absence of XAS data from the parent drugs in these fits points to profound changes in the coordination environments of Ru^III. The fits point to the presence of Ru^IV/III clusters and binding of Ru^III to S‐donor groups, amine/imine and carboxylato groups of proteins. Cellular uptake of KP1019 is approximately 20‐fold higher than that of NAMI‐A under the same conditions, but it diminishes drastically after the decomposition of KP1019 in cell‐culture media, which indicate that the parent complex is taken in by cells through passive diffusion.     

Transposition aspidospermane-eburnane : hemisynthese directe de derives apovincaminiques

Apovincamine 5a is synthetized in a one pot process from vincadifformine 1a via the chloro-16 indolenine 3 by heating in trifluoroacetic or formic acid; this process is extended to analogs of apovincamine, especially vinpocetine 5b.     

Efficiency of test for independence after Box-Cox transformation

We consider the efficiency and the power of the normal theory test for independence after a Box-Cox transformation. We obtain an expression for the correlation between the variates after a Box-Cox transformation in terms of the correlation on the normal scale. We discuss the efficiency of test of independence after a Box-Cox transformation and show that for the family considered it is always more efficient to conduct the test of independence based on Pearson correlation coefficient after transformation to normality. Power of test of independence before and after a Box-Cox transformation is studied for a finite sample size using Monte Carlo simulation. Our results show that we can increase the power of the normal-theory test for independence after estimating the transformation parameter from the data. The procedure has application for generating non-negative random variables with prescribed correlation.     

13C nmr spectroscopy of tetracarbocyclic diterpenes and related substances1

A caarbon shift analysis of hibaene, phyllocladene, cafestol, cafamarine, mascaroside and hilbane-like substances is presented.     

Femtosecond dynamics of isolated phenylcarbenes

Understanding the primary photophysical processes in molecules is essential for interpreting their photochemistry, because molecules rarely react from the initially excited electronic state. In this study the ultrafast excited-state dynamics of chlorophenylcarbene (CPC) and trifluoromethylphenylcarbene (TFPC), two species that are considered as models for carbene dynamics, were investigated by femtosecond time-resolved pump probe spectroscopy in the gas phase. Their dynamics was followed in real time by time-resolved photoionization and photoelectron imaging. CPC was excited at 265 nm into the 3 1A' state, corresponding to excitation from a pi-orbital of the aromatic ring into the LUMO. The LUMO contains a contribution of the p-orbital at the carbene center. Three time constants are apparent in the photoelectron images: A fast decay process with tau1 approximately 40 fs, a second time constant of tau2 approximatley 350 fs, and an additional time constant of tau3 approximately 1 ps. The third time constant is only visible in the time-dependence of low kinetic energy electrons. Due to the dense manifold of excited states between 3.9 and 5 eV, known from ab initio calculations, the recorded time-resolved electron images show broad and unstructured bands. A clear population transfer between the states thus can not directly be observed. The fast deactivation process is linked to either a population transfer between the strongly coupled excited states between 3.9 and 5.0 eV or the movement of the produced wave packet out of the Franck-Condon region. Since the third long time constant is only visible for photoelectrons at low kinetic energy, evidence is given that this time constant corresponds to the lifetime of the lowest excited A 1A' state. The remaining time constant reflects a deactivation of the manifold of states in the range 3.9-5.0 eV down to the A 1A' state.     

Highly conducting transmembrane pores formed by aromatic oligoamide macrocycles

Oligoamide macrocycles 1d and 1e, which carry membrane-compatible side chains and contain a hydrophilic, noncollapsible cavity, were found to mediate high ion flux across a lipid bilayer, as demonstrated by results from (23)Na NMR and planar bilayer conductance measurements. The measured transmembrane single channel currents are very high, rivaling those typically associated with pore-forming protein toxins. The obtained results have demonstrated the promise of developing large, highly conducting channels based on nanopores formed by oligoamide macrocycles.     

Expedient approach to chiral cyclobutanones: asymmetric synthesis of cyclobut-G

An efficient one-pot asymmetric synthesis of cyclobutanones from chiral enol ethers is described. The approach is illustrated with alkyl- and functionalized alkyl-substituted enol ethers (nine examples). A new enantioselective synthesis of cyclobut-G (Lobucavir) could thus be achieved.