Unsteady axisymmetric stagnation flow on a circular cylinder

Unsteady, axisymmetric stagnation flow about a circular cylinderis examined when the far-field flow is a periodic function oftime with a fixed time average and an oscillatory part of prescribedamplitude and frequency. Solutions are computed for arbitraryvalues of the Reynolds number, quantifying the effects of surfacecurvature, and a frequency parameter based on the period ofthe far-field flow. It is found that solutions remain regularand periodic provided that the far-field amplitude lies belowa critical value. Above this value, solutions terminate in afinite-time singularity. The blow-up time is delayed by increasingthe curvature of the surface. These results are corroboratedby asymptotic predictions valid in the limits of small and largeamplitude and frequency. For large Reynolds number, the problemreduces to the two-dimensional stagnation-point flow againsta plane wall studied by previous authors.     

GC-MS in space research: decoding complex isothermal chromatograms recovered from space missions

An analytical procedure is described to study GC-MS isothermal chromatograms simulating those recovered from space missions: in fact GC plays a predominant role in space missions devoted to characterizing the chemical composition of extra-terrestrial atmospheres. SIM (selected ion monitoring) detection was used for monitoring selected chemical classes: a simplified chromatogram can be obtained giving information on the chemical composition of the complex mixture. Since only isothermal GC chromatograms are allowed by flight constraints, a time axis transformation is required to make them homogeneous: i.e., constant retention increments for CH2 additions in terms of a homologous series. The order in the linearized chromatogram can be simply singled out with a chemometric approach based on the study of the Autocovariance Function (ACVF) computed on the digitized chromatogram: the plot of the experimental autocorrelation function (EACF) shows well-shaped peaks if constant interdistances are repeated in different regions of the chromatogram. The method was applied to standard mixtures representative of planetary atmospheres--hydrocarbons, nitriles and oxygenated compounds with between 3 and 12 carbon atoms--analyzed in flight simulating conditions. The coupling of the selectivity of SIM detection with the interpretation power of the EACF procedure proves to be a powerful tool for interpreting data recovered from space missions: the chemical composition of the mixture can be identified by handling the raw SIM chromatograms.     

Performance studies of a full-length prototype for the CASTOR forward calorimeter at the CMS experiment

The Time-Of-Flight detector (TOF) of the ALICE experiment at the CERN LHC is based on Multi-gap Resistive Plate Chambers (MRPCs). The TOF detector consists of 152928 readout channels covering a total area of 141 m². In this paper the results of the calibration with cosmic-ray data collected during 2009 are presented.     

Polyethylene glycol matrix reduces the rates of photochemical and thermal release of nitric oxide from S-nitroso-N-acetylcysteine

S -nitrosothiols have many biological activities and may act as nitric oxide (NO) carriers and donors, prolonging NO half-life in vivo. In spite of their great potential as therapeutic agents, most S -nitrosothiols are too unstable to isolate. We have shown that the S -nitroso adduct of N -acetylcysteine (SNAC) can be synthesized directly in aqueous and polyethylene glycol (PEG) 400 matrix by using a reactive gaseous (NO/O₂) mixture. Spectral monitoring of the S–N bond cleavage showed that SNAC, synthesized by this method, is relatively stable in nonbuf-fered aqueous solution at 25°C in the dark and that its stability is greatly increased in PEG matrix, resulting in a 28-fold decrease in its initial rate of thermal decomposition. Irradiation with UV light (λ= 333 nm) accelerated the rate of decomposition of SNAC to NO in both matrices, indicating that SNAC may find use for the photogeneration of NO. The quantum yield for SNAC decomposition decreased from 0.65 ± 0.15 in aqueous solution to 0.047 ± 0.005 in PEG 400 matrix. This increased stability in PEG matrix was assigned to a cage effect promoted by the PEG microenvironment that increases the rate of geminated radical pair recombination in the homolytic S–N bond cleavage process. This effect allowed for the storage of SNAC in PEG at −20°C in the dark for more than 10 weeks with negligible decomposition. Such stabilization may represent a viable option for the synthesis, storage and handling of S -nitrosothiol solutions for biomedical applications.     

Event-by-event fluctuation studies in the ALICE experiment

Event-by-event (E-by-E) fluctuations are considered to be one of the possible indications that a phase transition from ordinary hadronic matter to a plasma of quarks and gluons has occurred, as it is expected to happen in ultra-relativistic heavy-ion collisions. In this article, the results of a study concerning the observability of E-by-E fluctuations for the ALICE experiment at the LHC collider at CERN is presented. In particular, an estimate of the E-by-E statistical sensitivity in the measurement of the inverse slope parameter from the transverse momentum spectra of hadrons and of their particle ratios is discussed. The analysis relies on the excellent performance of ALICE in terms of particle identification.     

A computationally efficient finite element model with perfectly matched layers applied to scattering from axially symmetric objects

A frequency-domain finite-element (FE) technique for computing the radiation and scattering from axially symmetric fluid-loaded structures subject to a nonsymmetric forcing field is presented. The Berenger perfectly matched layer (PML), applied directly at the fluid-structure interface, makes it possible to emulate the Sommerfeld radiation condition using FE meshes of minimal size. For those cases where the acoustic field is computed over a band of frequencies, the meshing process is simplified by the use of a wavelength-dependent rescaling of the PML coordinates. Quantitative geometry discretization guidelines are obtained from a priori estimates of small-scale structural wavelengths, which dominate the acoustic field at low to mid frequencies. One particularly useful feature of the PML is that it can be applied across the interface between different fluids. This makes it possible to use the present tool to solve problems where the radiating or scattering objects are located inside a layered fluid medium. The proposed technique is verified by comparison with analytical solutions and with validated numerical models. The solutions presented show close agreement for a set of test problems ranging from scattering to underwater propagation.     

Capillary electrophoresis–electrospray mass spectrometry and HR–ICP–MS for the detection and quantification of 10B-boronophenylalanine (10B–BPA) used in boron neutron capture therapy

Boron neutron capture therapy (BNCT) is a bimodal radiotherapeutic treatment based on the irradiation of neoplastic tissues with neutrons after the tissues have selectively accumulated molecules loaded with nuclides with large neutron capture cross-sections (such boron-10). Boron-10 carriers have been tested to a limited extent, and clinical trials have been conducted on sulfhydryl borane (¹⁰B-BSH) and boronophenylalanine (¹⁰B-BPA). However, precise and accurate measurements of boron-10 concentrations (0.1–100 μg/g) in specimens and samples of limited size (μg scale) are needed in order to be able to biologically characterise new compounds in predictive tissue dosimetry, toxicology and pharmacology studies as well as in clinical investigations. A new approach based on fast separation and detection of ¹⁰B-BPA performed by coupling capillary electrophoresis to electrospray mass spectrometry is reported. This method allows the quantitative analysis and characterisation of ¹⁰B-BPA in a short time with a high separation efficiency. Detection limits of 3 μM for ¹⁰B-BPA and 30 ng/mL for ¹⁰B were obtained with CE–ESI–MS. A quantification limit of 10 μM for ¹⁰B-BPA (100 ng/mL for ¹⁰B) was attained. The total boron-10 concentration was determined by high-resolution inductively coupled mass spectrometry in order to validate the method. Boron-10 isotope measurements were carried out by HR–ICP–MS at medium resolution (R=4000) due to the presence of an isobaric interference at mass 10. Good agreement was obtained between the values from CE–ESI–MS and those from HR–ICP–MS. The method has been successfully used to determine the ¹⁰B-BPA in two lines of cultured cells.     

A supramolecular approach to sub-ppb aromatic VOC detection in air

Micromachining technology is coupled to a selective pre-concentration material for the development of a portable sub-ppb level monitoring system for aromatic volatile organic compounds (VOC); the high sensitivity of Metal Oxide (MOX) gas sensors is combined with a supramolecular concentration unit to increase selectivity and reduce the detection limits.     

Gas chromatography-mass spectrometry analysis of amino acid enantiomers as methyl chloroformate derivatives: application to space analysis

This work describes a GC-MS method for enantioselective separation of amino acids. The method is based on a derivatization reaction which employs a mixture of alkyl chloroformate-alcohol-pyridine, as reagents to obtain the N(O,S)-alkyl alkoxy carbonyl esters of amino acids. Various reaction parameters are investigated and optimized to achieve a reproducible derivatization procedure suitable for separation of amino acid enantiomers on Chirasil-L-Val chiral stationary phase. In particular, the following topics are investigated for 20 proteinogenic amino acids: (i) the proper reagent and reaction conditions to obtain the highest derivative yield; (ii) the amino acid reactivity and the MS properties of the obtained derivatives; (iii) the linearity and sensitivity of the analytical method; (iv) the retention behavior of the derivatives and their enantiomeric separation on the Chirasil-L-Val chiral stationary phase. By combining the resolution power of the Chirasil-L-Val column and the high selectivity of the SIM MS detection mode, the described procedure enables the enantiomeric separation and quantification of 16 enantiomeric pairs of amino acids. The procedure is simple and fast and reproducible. It displays a wide linearity range at ppb detection limits for quantitative determinations: these properties make this derivatization method a suitable candidate for amino acid GC-MS analysis on board of the spacecrafts in space exploration missions of solar system body environments.