Prediction of Turbulence-Generated Secondary Mean Flow in a Square Duct

Near-wall second-moment closures have revealed a tendency to severely underpredict the strength of the turbulence-generated secondary flow in noncircular ducts. The aim of this study has been to elucidate the reasons for this failure that seems to be present at both high and low Reynolds numbers. Fully developed three-componential turbulent flow inside a straight square duct has been computed with the quasi-linear SSG second-moment closure and near-wall effects were modeled by elliptic relaxation. The results compared favourably with the reference DNS data, except that the strength of the turbulence-induced secondary flows is significantly underpredicted. A close examination of the generation mechanisms of the mean streamwise vorticity revealed that this discrepancy can be attributed to the secondary shear-stress component, the importance of which is generally overlooked. The normal-stress anisotropy was, however, adequately returned by the model and so was the variation of the friction velocity with Reynolds number over a wide Reynolds-number range. The present study supports the view that the wall-function approach should be abandoned in order to retain a physical appealing representation of the generation mechanisms of mean streamwise vorticity along internal corners. This revised version was published online in July 2006 with corrections to the Cover Date.     

Optimization of immunoaffinity enrichment and detection: toward a comprehensive characterization of the phosphotyrosine proteome of K562 cells by liquid chromatography-mass spectrometry

Phosphorylation of protein tyrosine residues regulates many cell functions and has also been proved to be involved in oncogenesis. Thus, the identification of the phosphotyrosine (pTyr) proteome of cells is a very important task. Since tyrosine phosphorylation represents only around 1% of the total human phosphoproteome, the study of pTyr proteins is rather challenging. Here we report the optimization study of the phosphotyrosine proteome using K562 cells as a model system. A substantial segment of the phosphotyrosine proteome of K562 cells was characterized by immunoaffinity enrichment with 4G10 and PYKD1 antibodies followed by LC-MS/MS analysis. 480 non-redundant pTyr peptides corresponding to 342 pTyr proteins were found. 141 pTyr peptides were not described elsewhere. The mass spectrometry approach involving high-resolving FTMS analysis of precursor ions and subsequent detection of CID fragments in a linear ion trap was considered as optimal. For detection of low abundant pTyr peptides pooling of individual immunoaffinity enrichments for one LC-MS/MS analysis was crucial. The enrichment properties of the monoclonal PYKD1 antibody were presented for the first time, also in comparison to the 4G10 antibody. PYKD1 was found to be more effective for protein enrichment (1.2 and 5% efficiency at peptide and protein level correspondingly), while 4G10 showed better results when peptide enrichment was performed (15% efficiency versus 3.6% at protein level). Substantially different subsets of the phosphoproteome were enriched by these antibodies. This finding together with previous studies demonstrates that comprehensive pTyr proteome characterization by immunoprecipitation requires multiple antibodies to be used for the affinity enrichment.     

Rotational coherence imaging and control for CN molecules through time-frequency resolved coherent anti-Stokes Raman scattering

Numerical wave packet simulations are performed for studying coherent anti-Stokes Raman scattering (CARS) for CN radicals. Electronic coherence is created by femtosecond laser pulses between the X(2)Σ and B(2)Σ states. Due to the large energy separation of vibrational states, the wave packets are superpositions of rotational states only. This allows for a specially detailed inspection of the second- and third-order coherences by a two-dimensional imaging approach. We present the time-frequency domain images to illustrate the intra- and intermolecular interferences, and discuss the procedure to rationally control and experimentally detect the interferograms in solid Xe environment.     

The state of carboxymethylated nanofibrils after homogenization-aided dilution from concentrated suspensions: a rheological perspective

The rheological properties of a carboxymethylated (D.S. ≈ 0.1) nanofibrillated cellulose (NFC) were investigated at different solid contents. The critical overlap concentration was determined to be in the range between 0.04 and 0.07 % (w/w) using shear stress versus shear rate measurements. From the critical overlap concentration using the simple Mason excluded volume formalism, the apparent aspect ratio was estimated to be 75 [at a critical overlap concentration of 0.04 % (w/w)]. The aspect ratio of the NFC system was also estimated by using the Einstein–Simha equation together with the intrinsic viscosity value of the system (corrected for the electroviscous effects). The obtained value was found to be around 80, which is in good agreement with the value obtained from the excluded volume calculation. Further, by combining oscillatory measurements and the equation of Shankar et al. the apparent fibril length was determined to be 4 µm. As the production of NFC through homogenization occurs at concentrations far above the critical overlap concentration an NFC-gel is constituted by a severely entangled structure. The disentanglement of the fibrils is therefore difficult and the employed dilution method was found not to lead to fully liberated nanofibrils, which was also indicated by atomic force microscopy-imaging.     

Determination of phosphonoformate (foscarnet) in biological fluids by ion-pair reversed-phase liquid chromatography

Bioanalytical liquid chromatographic methods for the determination of phosphonoformate (foscarnet) have been developed. Biological fluids, after simple pre-treatment (ultrafiltration and/or treatment with charcoal), were injected into a reversed-phase liquid chromatographic system with electrochemical detection. Foscarnet was retained as an ion pair with tetrahexylammonium; addition of pyrophosphate was necessary in order to obtain an acceptable peak. This additive could also be used for the fine regulation of the retention to achieve the necessary selectivity.     

In situ characterization of an iron catalyst by potassium ion desorption and electron emission measurements

The surface conditions of an industrial iron catalyst were monitoredin situ by work function measurements and measurements of thermal desorption of potassium ions. Changes in activation energy for potassium ion desorption and in work function values during catalyst activation and deactivation are discussed in terms of the potassium coverage and chemical composition of the catalyst surface.