MS-Express: data-extracting and -processing software for high-throughput experimentation with mass spectrometry

High-throughput experiments (HTE) result in large amounts of raw data that have to be evaluated for sample classification. Especially mass spectrometry, a widely used detection method in catalytic HTE applications, produces enormous amounts of data. In the past few years, in catalysts research, several test rigs based on mass spectrometric detection have been independently reported by different groups. In a typical HTE, the catalysts are tested sequentially; the recording of the scans, however, occurs continuously. For this reason, the scans of interest have to be extracted from the raw data, and scans belonging to the same sample have to be averaged in a tedious procedure before further processing. In this publication, we present our custom-designed software MS-Express (mass spectrometry data-extracting and -processing software), an efficient tool for HTE MS data evaluation. MS-Express not only sorts the data, it also establishes statistical significance with the help of reference and blank data and provides concise information about abundance and intensity distributions of expected peaks. A special feature is that the program also reports unexpected MS signals, which potentially lead to unexpected discoveries.     

Interface‐fitted moving mesh method for axisymmetric two‐phase flow in microchannels

A boundary‐fitted moving mesh scheme is presented for the simulation of two‐phase flow in two‐dimensional and axisymmetric geometries. The incompressible Navier‐Stokes equations are solved using the finite element method, and the mini element is used to satisfy the inf‐sup condition. The interface between the phases is represented explicitly by an interface adapted mesh, thus allowing a sharp transition of the fluid properties. Surface tension is modelled as a volume force and is discretized in a consistent manner, thus allowing to obtain exact equilibrium (up to rounding errors) with the pressure gradient. This is demonstrated for a spherical droplet moving in a constant flow field. The curvature of the interface, required for the surface tension term, is efficiently computed with simple but very accurate geometric formulas. An adaptive moving mesh technique, where smoothing mesh velocities and remeshing are used to preserve the mesh quality, is developed and presented. Mesh refinement strategies, allowing tailoring of the refinement of the computational mesh, are also discussed. Accuracy and robustness of the present method are demonstrated on several validation test cases. The method is developed with the prospect of being applied to microfluidic flows and the simulation of microchannel evaporators used for electronics cooling. Therefore, the simulation results for the flow of a bubble in a microchannel are presented and compared to experimental data.     

Inequalities and equalities for ℓ = 2 (Sylvester), ℓ = 3 (Frobenius), and ℓ > 3 matrices

This paper gives simple proofs of the Sylvester (? = 2) and Frobenius (? = 3) inequalities. Moreover, a new sufficient condition for the equality of the Frobenius inequality is provided. In addition, an extension for ? > 3 matrices and an application to generalized inverses are provided.     

True moving bed electrophoresis using stepped electric field gradients

True moving bed electrophoresis has been shown to be an effective technique for the bench-scale separation of enantiomers, and it is desired to increase the maximum possible throughput attainable with the process by using electric field gradients. Homatropine enantiomer separations were performed and results using a stepped electric field gradient were compared to those using a traditional non-gradient separation. In order to accomplish this, a newly designed stator was constructed for use with the Vortex-Stabilized Electrophoresis Apparatus that has three sets of electrode housings, one set at both ends and one in the middle of the chamber. There were several problems related to the membranes used at the middle electrode. The dialysis membranes were permeable to the homatropine enantiomers, and while a switch to anion exchange membranes prevented the permeation of the homatropine, this caused a pH shift that interrupted binding to the hydroxypropyl-ss-cyclodextrin chiral selector. These problems prevented any meaningful data from being collected using homatropine enantiomers, and due to this, a proof of concept study was conducted using two bovine proteins. The separations using fluorescein-labeled BSA and bovine hemoglobin showed that a 63% increase in the maximum processing rate was attainable. The maximum throughput using the non-gradient process was 30.6 mg/h and the maximum was 50.0 mg/h using an electric field gradient that was 10% lower than the non-gradient field in section II and 10% higher in section III.     

Continuous voltage gradients and their application to true moving bed electrophoresis

Gradient elution has been practiced in chromatographic separations for many years. The application of discontinuous "step" gradients in simulated moving bed (SMB) chromatography has been very successful in increasing both processing rates and column productivity, resulting in a reduction in the number of SMB columns required. With the advent of the field gradient focusing techniques, electrophoresis has gained the ability to apply a continuous electric field gradient to a true moving bed (TMB) electrophoretic separation. Application of a spatial gradient allows a large degree of control of the product concentrations inside the separation unit as well as a large increase in product throughput. A model of moving bed electrophoretic separations has been developed that demonstrates the potential advantages of applying a continuous gradient to the moving bed process. These advantages include the reduction of detrimental peak tailing and the ability to decrease the concentrations of the compounds being separated in comparison with commonly used step gradient elution.     

Status of prediction methods for critical heat fluxes in mini and microchannels

Saturated critical heat flux (CHF) is an important issue during flow boiling in mini and microchannels. To determine the best prediction method available in the literature, 2996 data points from 19 different laboratories have been collected since 1958. The database includes nine different fluids (R-134a, R-245fa, R-236fa, R-123, R-32, R-113, nitrogen, CO₂ and water) for a wide range of experimental conditions. This database has been compared to 6 different correlations and 1 theoretically based model. For predicting the non-aqueous fluids, the theoretical model by Revellin and Thome [Revellin, R., Thome, J.R., 2008. A theoretical model for the prediction of the critical heat flux in heated microchannels. Int. J. Heat Mass Transfer 51, 1216–1225] is the best method. It predicts 86% of the CHF data for non-aqueous fluids within a 30% error band. The data for water are best predicted by the correlation by Zhang et al. [Zhang, W., Hibiki, T., Mishima, K., Mi, Y., 2006. Correlation of critical heat flux for flow boiling of water in minichannels. Int. J. Heat Mass Transfer 49, 1058–1072]. This method predicts 83% of the CHF data for water within a 30% error band. Some suggestions have also been proposed in this paper for the future studies.     

Application of a resolution enhancement technique to the FTIR characterisation of propylene/ethylene copolymers

FTIR methods for determining the composition and ethylene sequencing in propylene/ethylene copolymers are presented and quantified by comparison to¹³C NMR data.     

Demonstration of a high-speed nonscanning imaging spectrometer

We report results from a field demonstration of a nonscanning high-speed imaging spectrometer [computed-tomography imaging spectrometer (CTIS)] capable of simultaneously recording spatial and spectral information about a rapidly changing scene. High-speed spectral imaging was demonstrated by collection of spectral and spatial snapshots of a missile in flight. This instrument is based on computed-tomography concepts and operates in the visible spectrum (430-710nm). Raw image data were recorded at video frame rate (30frames / s) and an integration time of 2ms. An iterative reconstruction of the spatial and spectral scene information from each raw image took 10s. We present representative missile spectral signatures from the missile firing. The accuracy of the high-speed spectrometer is demonstrated by comparison of extended-source static-scene spectra acquired by a nonimaging reference spectrometer with spectra acquired by use of CTIS imaging of the same static scenes.     

Continuous fractionation of enantiomer pairs in free solution using an electrophoretic analog of simulated moving bed chromatography

Continuous fractionation of the left and right enantiomers of Piperoxan was performed in free solution in a vortex-stabilized electrophoresis apparatus. Sulfated beta-cyclodextrin was used as the chiral selector. A capillary electrophoresis (CE) study of the separation of Piperoxan enantiomers was carried out in order to find the buffer conditions that produce the maximum peak separation time between the two enantiomers and the optimal chiral selector concentration. These peak separation times were then used to calculate the electrophoretic mobilities of the enantiomer-ligand complexes. The difference in electrophoretic mobilities, when used in a preliminary model of the enantiomer separation, indicated that, by imposing a fluid flow opposite the direction of electromigration, it would be possible to force the fast and slow enantiomers to move in opposite directions within the vortex-stabilized apparatus. Using the predictions of the preliminary separation model, the vortex stabilized electrophoresis apparatus was configured with a feed port at the center of the chamber axis and offtake ports near the cathode and anode. This allowed for continuous operation of the apparatus. Continuous fractionations were completed at throughputs of 1.5 and 4.0 mg/h with both offtakes showing greater than 99% enantiomeric purity at 4.0 mg/h using CE. Fractionation was achieved at a throughput of 10 mg/h, but while the slow enantiomer was recovered with greater than 99% purity, only 96% enantiomeric purity of the fast stereoisomer was achieved. The loss of resolution at higher volumetric throughputs supports our hypothesis that a mobility-dependent "window" of operation exists in which two solutes can be completely separated.     

Alkylation of aromatics on p-containing ZSM-5 zeolites

The catalytic activity of ZSM-5 zeolites, modified with phosphorus compounds, has been studied in benzene and toluene alkylation by ethylene. Concentration of acid sites of different nature in the samples was characterized by IR spectroscopy of OH-groups and adsorbed CO. Modification was shown to decrease the concentrations of both strong protic and non-aprotic sites. New acid sites are assumed to appear in P-containing zeolites. The strength of acid sites in the zeolites is supposed to follow the sequence:[[SiOAl]H][POH]> >[MgOH. Activity and regioselectivity of P-containing zeolites are considered to depend on the nature and concentration of the acid sites.