Enantioselective capillary electrochromatography: recent developments and new trends

Since its development in the early 1970s, CEC has been studied quite extensively, but unfortunately its use is still mostly located at an academic level. Reasons for this are the limited availability of commercially available stationary phases (SPs) and columns, along with some practical limitations, such as column fragility, lack of column robustness and reproducibility. Nevertheless, CEC maintains a place among the separation techniques, probably because of its unique feature to combine two separation principles. Also in the field of chiral separations, CEC is often used as a separation technique and already showed its potential for this kind of analyses. This overview will focus on the recent applications, i.e. between 2006 and 2010, in enantioselective analysis by means of CEC. For the selected applications, the used SPs (chiral selectors) and their potential for future method development or screening purposes will be evaluated and critically discussed.     

Simulation of Premixed Turbulent Combustion in a Gas Engine using the Immersed Boundary Method and a Level Set Flame Model

An efficient simulation approach for turbulent flame brush propagation is a level set formulation closed by the turbulent flame speed. A formulation of the level set equation with the corresponding treatment of the turbulent mass burning rate that is compatible with standard Finite Volume discretization schemes available in computational fluid dynamics codes is employed. In order to simplify and to speed up the meshing process in complicated geometries (here in gas engines) the immersed boundary method in a continuous formulation, where the forces replacing the boundaries are introduced in the momentum conservation equations before discretization, is employed. In our contribution, aspects of the numerical implementation of the level set flame model combined with the immersed boundary formulation in OpenFOAM are presented. First representative simulation results of a homogeneous methane/air mixture combustion in a simplified engine geometry are shown. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ti-mediated intramolecular cyclopropanation of N-alkenyl thioamides: scope and mechanistic study

Although thioamides generally undergo a reductive alkylation process when they are treated with a Grignard reagent in the presence of Ti(OiPr)₄, substrates fitted with a but-3-enyl substitution at the nitrogen atom are shown to be converted into bicyclic aminocyclopropanes. These reactions are compared with the similar cyclisations of the corresponding carboxylic amide substrates. A mechanistic study is provided. Coincidently, new reagent systems are identified for the mediation of the same transformation.     

An Electrochemical Study of Bis(cyclopentadienyl)titanium(IV) Dichloride in the Presence of Magnesium Ions,Amides or Alkynes

Russian Journal of Electrochemistry - In tetrahydrofuran, the electrochemical reduction of Cp2TiIVCl2 (2 mM) generated three titanium(III) complexes which were in equilibrium:...     

Magnetic control of natural convection in the horizontal Bridgman configuration: symmetric and non-symmetric cross sections

This study deals with the electromagnetic damping of free-convective flows in cavities such as those used in the crystal growth horizontal Bridgman configuration. The cavities are filled with a dilute electrically conducting alloy and are subjected to a horizontal temperature gradient. The flow is steady and laminar under an external, vertical, transversal and uniform magnetic field. Several cross sections of the cavities were investigated and can either be centro-symmetric or not. The governing equations for such problems are two coupled partial differential equations, for the velocity and the induced magnetic fields, coupled with a third integral equation for mass conservation. A finite element method has been developed, and the numerical results for the variation of the velocity and the induced magnetic field in terms of the Hartmann number show a considerable decrease in convection intensity as the Hartmann number increases. Results also reveal the presence of the well-known Hartmann and parallel layers. For non-centro-symmetric sections, results show the way the flow reorganises into two cells as the Hartmann number increases.     

Assessing the suitability of capillary electrophoresis‐mass spectrometry for biomarker discovery in plasma‐based metabolomics

The actual utility of capillary electrophoresis‐mass spectrometry (CE‐MS) for biomarker discovery using metabolomics still needs to be assessed. Therefore, a simulated comparative metabolic profiling study for biomarker discovery by CE‐MS was performed, using pooled human plasma samples with spiked biomarkers. Two studies have been carried out in this work. Focus of study I was on comparing two sets of plasma samples, in which one set (class I) was spiked with five isotope‐labeled compounds, whereas another set (class II) was spiked with six different isotope‐labeled compounds. In study II, focus was also on comparing two sets of plasma samples, however, the isotope‐labeled compounds were spiked to both class I and class II samples but with concentrations which differ by a factor two between both classes (with one compound absent in each class). The aim was to determine whether CEMS‐based metabolomics could reveal the spiked biomarkers as the main classifiers, applying two different data analysis software tools (MetaboAnalyst and Matlab). Unsupervised analysis of the recorded metabolic profiles revealed a clear distinction between class I and class II plasma samples in both studies. This classification was mainly attributed to the spiked isotope‐labeled compounds, thereby emphasizing the utility of CE‐MS for biomarker discovery.     

The preparation of octahydro leukotrienes C,D, and E via a stereoselective sulfenyllactonization reaction

Sulfenyl halides derived from the N-trifluoroacetamido methyl ester derivatives of cysteine, cysteinyiglycine and glutathione react stereoselectively with (5E)- and (5Z)-eicosenoic acids to provide, after separation of diastereomers and hydrolysis of the protecting groups, the fully saturated analogues of leukotrienes LTC₄, LTD₄, and LTE₄.     

Combination of gas chromatography-mass spectrometry and mass spectral deconvolution for structural elucidation of an unusual C29-steroid detected in a complex sedimentary matrix

A complex sedimentary sample from the Monterey Formation (CA, USA) has been submitted to GC-MS analysis followed by mass spectral deconvolution using Automated Mass Spectral Deconvolution and Identification System (AMDIS). Adjusting the parameters of the software allowed for the extraction of the spectrum of an unusual steroidal hydrocarbon coeluting with the major compound of the chromatogram. Following a careful interpretation of the "extracted" mass spectrum, the structure of the unknown has been postulated to be the 4,14-dimethylcholestane (DMC). Possible origins of this rare steroid are briefly discussed. Thus, application of AMDIS appears to be particularly suitable for the GC-MS analysis of natural complex mixtures characterized by a high number of analytes present in low amounts.     

Studies on the intramolecular Kulinkovich-de Meijere reaction of disubstituted alkenes bearing carboxylic amide groups

1,2-Disubstituted olefins bearing an acetamide group were found to undergo intramolecular Kulinkovich-de Meijere cyclopropanation in moderate yield but almost complete diastereoselectivity.