Differential MRI diagnosis between brain abscesses and necrotic or cystic brain tumors using the apparent diffusion coefficient and normalized diffusion-weighted images

Magnetic Resonance Diffusion-Weighted Imaging (DWI) has been reported to be helpful for the differential diagnosis between abscesses and cystic/necrotic brain tumors. However the number of patients is still limited, and the sensitivity and specificity of the method remain to be confirmed. The primary purpose of this study was to investigate a larger sample of patients, all investigated under the same experimental conditions, in order to obtain statistically significant data. Moreover, there is no consensus about the appropriate values of b required to use to make an accurate diagnosis from DWI. The secondary purpose of this study was to determine the discriminating threshold b values for raw diffusion-weighted images and for normalized diffusion-weighted images. On the basis of 14 abscesses, 10 high-grade gliomas and 2 metastases, we show that the calculation of accurate Apparent Diffusion Coefficient (ADC) values gives a specificity rate of 100%. Without ADC calculation, we show that image normalization is required to make an accurate differential diagnosis, and we highlight the ability of DWI to discriminate between brain abscesses and cystic/necrotic brain tumors using normalized signal intensity at lower b values (503 s/mm(2)) than usual.     

Direct numerical simulation of the flow around a wall-mounted square cylinder under various inflow conditions

The flow around a wall-mounted square cylinder of side d is investigated by means of direct numerical simulation (DNS). The effect of inflow conditions is assessed by considering two different cases with matching momentum-thickness Reynolds numbers Re_θ ? 1000 at the obstacle: the first case is a fullyturbulent zero pressure gradient boundary layer, and the second one is a laminar boundary layer with prescribed Blasius inflow profile further upstream. An auxiliary simulation carried out with the pseudo-spectral Fourier–Chebyshev code SIMSON is used to obtain the turbulent time-dependent inflow conditions which are then fed into the main simulation where the actual flow around the cylinder is computed. This main simulation is performed, for both laminar and turbulent-inflows, with the spectral-element method code Nek5000. In both cases the wake is completely turbulent, and we find the same Strouhal number St ? 0.1, although the two wakes exhibit structural differences for x > 3d downstream of the cylinder. Transition to turbulence is observed in the laminar-inflow case, induced by the recirculation bubble produced upstream of the obstacle, and in the turbulent-inflow simulation the streamwise fluctuations modulate the horseshoe vortex. The wake obtained in our laminar-inflow case is in closer agreement with reference particle image velocimetry measurements of the same geometry, revealing that the experimental boundary layer was not fully turbulent in that dataset, and highlighting the usefulness of DNS to assess the quality of experimental inflow conditions.     

Aryl aldehydes as traceless dielectrophiles in bifunctional titanocene-catalyzed propargylic C-X activations

The titanocene-catalyzed construction of all-carbon substituted tertiary centers directly from aromatic aldehydes is described. The starting aldehyde behaves as a traceless functionality in the formation of multiple carbon-carbon bonds through consecutive carbon-heteroatom bond activations. The sequential addition of a metal acetylide and a second carbon nucleophile to the dielectrophilic aldehyde enables the construction of symmetrical and unsymmetrical 1,4-diynes in good yields.     

Gold(I)-catalyzed formation of 3-pyrazolines through cycloaddition of diaziridine to alkynes

This work reports the high-yield formation of pyrazoline derivatives mediated by gold(I) catalysts. The reaction utilizes a diaziridine, which has seen only limited usage in organic methodology. Mechanistic studies suggest a gold-mediated opening of the diazridine ring, alkyne insertion, and finally an intramolecular hydroamination to furnish the product.     

Validation of a novel LC-MS/MS method for the quantitation of colistin A and B in human plasma

A liquid chromatography/tandem mass spectrometry (LC-MS/MS) method, characterized by complete automation and high-throughput, was developed for the determination of colistin A and B in human plasma. All sample preparation procedures were performed by using 2.2 mL 96-deep-well plates, whereas robotic liquid-handling workstations were utilized for all liquid transfer steps, including solid-phase extraction (SPE). The whole preparation procedure was very rapid, whereas the method had a very short chromatographic run time of just 2 min. Sample analysis was performed by reversed phase LC-MS/MS, with positive electrospray ionization, using multiple reaction monitoring. The absence of available purified colistin A and B standards led to the development of a novel LC method with evaporative light-scattering detector for the determination of their stoichiometries in the standard mixture, along with its purity. The proposed bioanalytical method was fully validated and it was proven to be selective, accurate, precise, reproducible and suitable for the determination of colistin A and B in human plasma. It was applied successfully to a pharmacokinetic study for the determination of both analytes in samples of patients.     

Comparison of AOAC 2005.06 LC official method with other methodologies for the quantitation of paralytic shellfish poisoning toxins in UK shellfish species

A refined version of the pre-column oxidation liquid chromatography with fluorescence detection (ox-LC-FLD) official method AOAC 2005.06 was developed in the UK and validated for the determination of paralytic shellfish poisoning toxins in UK shellfish. Analysis was undertaken here for the comparison of PSP toxicities determined using the LC method for a range of UK bivalve shellfish species against the official European reference method, the PSP mouse bioassay (MBA, AOAC 959.08). Comparative results indicated a good correlation in results for some species (mussels, cockles and clams) but a poor correlation for two species of oysters (Pacific oysters and native oysters), where the LC results in terms of total saxitoxin equivalents were found to be on average more than double the values determined by MBA. With the potential for either LC over-estimation or MBA under-estimation, additional oyster and mussel samples were analysed using MBA and ox-LC-FLD together with further analytical and functional methodologies: a post-column oxidation LC method (LC-ox-FLD), an electrophysiological assay and hydrophilic interaction liquid chromatography with tandem mass spectrometric detection. Results highlighted a good correlation among non-bioassay results, indicating a likely cause of difference was the under-estimation in the MBA, rather than an over-estimation in the LC results.     

Metabolic fingerprinting as a tool to monitor whole-cell biotransformations

Fourier transform infrared (FT-IR) spectroscopy was employed as a rapid high-throughput phenotypic typing technique to generate metabolic fingerprints of Escherichia coli MG1655 pDTG601A growing in fed-batch culture, during the dioxygenase-catalysed biotransformation of toluene to toluene cis-glycol. With toluene fed as a vapour, the final toluene cis-glycol concentration was 83 mM, whereas the product concentration was only 22 mM when the culture was supplied with liquid toluene. Multivariate statistical analysis employing cluster analysis was used to analyse the dynamic changes in the data. The analysis revealed distinct trends and trajectories in cluster ordination space, illustrating phenotypic changes related to differences in the growth and product formation of the cultures. In addition, partial least squares regression was used to correlate the FT-IR metabolic fingerprints with the levels of toluene cis-glycol and acetate, the latter being an indicator of metabolic stress. We propose that this high-throughput metabolic fingerprinting approach is an ideal tool to assess temporal biochemical dynamics in complex biological processes, as demonstrated by this redox biotransformation. Moreover, this approach can also give useful information on product yields and fermentation health indicators directly from the fermentation broth without the need for lengthy chromatographic analysis of the products.     

Influence of montmorillonite tactoid size on Na-Ca cation exchange reactions

The spatial organisation of swelling clay platelets in a suspension depends on the chemical composition of the equilibration solution. Individual clay platelets can be well dispersed, with surfaces entirely in contact with the external solution, or be stacked in tactoids, where part of the surfaces forms parallel alignments embedding interlayer water and cations. External and interlayer surfaces do not exhibit similar affinities for cations having different hydration and charge properties and the clay platelet stacking arrangement influences the clay affinity for these cations. This paper aims to establish the link between exchange properties and clay tactoid size and organisation for Na-Ca exchange on montmorillonite. Different montmorillonite samples behave differently with regards to Na-Ca exchange, from ideal to non-ideal exchange behaviour. A simple model coupling the tactoid stacking size to different Na/Ca relative affinities of the external and interlayer clay surfaces enables these differences to be reproduced.