Microchip atmospheric pressure chemical ionization source for mass spectrometry

A novel microchip heated nebulizer for atmospheric pressure chemical ionization mass spectrometry is presented. Anisotropic wet etching is used to fabricate the flow channels, inlet, and nozzle on a silicon wafer. An integrated heater of aluminum is sputtered on a glass wafer. The two wafers are jointed by anodic bonding, creating a two-dimensional version of an APCI source with a sample channel in the middle and gas channels symmetrically on both sides. The ionization is initiated with an external corona-discharge needle positioned 2 mm in front of the microchip heated nebulizer. The microchip APCI source provides flow rates down to 50 nL/min, stable long-term analysis with chip lifetime of weeks, good quantitative repeatability (RSD < 10%) and linearity (r(2) > 0.995) with linear dynamic rage of at least 4 orders of magnitude, and cost-efficient manufacturing. The limit of detection (LOD) for acridine measured with microchip APCI at flow rate of 6.2 muL/min was 5 nM, corresponding to a mass flow of 0.52 fmol/s. The LOD with commercial macro-APCI at a flow rate of 1 mL/min for acridine was the same, 5 nM, corresponding to a significantly worse mass flow sensitivity (83 fmol/s) than measured with microchip APCI. The advantages of microchip APCI makes it a very attractive new microfluidic detector.     

Gaschromatographie des Isopropanol-?thanol-Methanol-Wassersystems

Zusammenfassung Zum Nachweis von Isopropanol bei gleichzeitiger Anwesenheit von Methanol, Äthanol und Wasser wurde eine gaschromatographische Methode entwickelt. Die für diesen Zweck günstige Gesamtlänge der Kolonne beträgt 2,84 m, wovon der 2,24 m lange Anfangsteil mit Paraffinphase und der 0,6 m lange Schlußteil mit Polyäthylenglykolphase gefüllt ist. Als empfehlenswerte Temperatur für die Chromatographierung wird 47° C angegeben, wobei die Retentionszeiten für Methanol 12,1 min, für Äthanol 20,0 min, für Isopropanol 25,0 min und für Wasser 36 min betragen. Die Methode eignet sich ebenfalls gut zur quantitativen Bestimmung kleiner Äthanolmengen (1–3 Gew.-%) in Isopropanol.     

Development of LC/MS/MS methods for cocktail dosed Caco-2 samples using atmospheric pressure photoionization and electrospray ionization

Good reliability of Caco-2 permeability studies requires competent sampling and analytical methods to ensure the comparability of day-to-day experiments. In this work, two n-in-one LC/MS/MS methods based on two different ionization techniques were developed and validated for a group of reference compounds; eight of them are recommended by the Food and Drug Administration (FDA) for the evaluation of oral drug permeability. The performance of a new ionization technique, atmospheric pressure photoionization (APPI), as an interface for quantitative LC/MS analysis was evaluated in comparison to the electrospray ionization (ESI). Generally, the validation parameters, including sensitivity, accuracy, and repeatability, were comparable for the APPI and ESI methods. The main difference was that the linear quantitative range of APPI was 3-4 orders of magnitude (r(2) >/= 0.998) whereas in ESI it was typically 2-3 orders of magnitude (r(2) >/= 0.990). By the APPI and ESI methods, the simultaneous analysis of nine highly heterogeneous compounds was achieved within 5.5-7 min, which leads to significant savings in time and cost of the analyses. The successful validation data indicate the usefulness of both the methods for the rapid and sensitive (LOD values typically 相似文献   

Polynomial-Based Interpolation Filters—Part I: Filter Synthesis

This paper introduces a generalized design method for polynomial-based interpolation filters. These filters can be implemented by using a modified Farrow structure, where the fixed finite impulse response (FIR) sub-filters possess either symmetrical or anti-symmetrical impulse responses. In the proposed approach, the piecewise polynomial impulse response of the interpolation filter is optimized directly in the frequency domain using either the minimax or least mean square criterion subject to the given time domain constraints. The length of the impulse response and the degree of the approximating polynomial in polynomial intervals can be arbitrarily selected. The optimization in the frequency domain makes the proposed design scheme more suitable for various digital signal processing applications and enables one to synthesize interpolation filters for arbitrary desired and weighting functions. Most importantly, the interpolation filters can be optimized in a manner similar to that of conventional linear-phase FIR filters.     

ANN modeling applied to NO x reduction with octane in a new microreactor

A silver/alumina catalyst was tested for its NO _x reduction activity during oxygen-rich conditions and during variation in the input parameters (nitric oxide, octane and oxygen). The experimental data using the microreactor was investigated by means of artificial neural networks (ANN).     

Hydrogenolysis of Hydroxymatairesinol Over Carbon-Supported Palladium Catalysts

The natural lignan hydroxymatairesinol was hydrogenolysed to a potential anticarcinogenic substance matairesinol over different carbon-supported palladium catalysts. The reaction was conducted in 2-propanol at 70 °C under hydrogen flow in a stirred glass reactor. The catalysts were characterised by N₂-physisorption, CO pulse chemisorption and pH measurement of aqueous catalyst slurries. The most active catalyst (Degussa-Hüls) gave yields of matairesinol over 90% in 4 h. It was concluded that the acidity of the catalyst had a profound influence on the reaction rate.     

The redundancy of two three-state devices

The reliabilities of a three-state device and redundant structures of two such devices are considered, and it is shown that although the two failure modes were equally probable there may be advantages in using redundancy of two devices in series or parallel. It is also shown that the optimal redundant structure of two devices is not solely dependent on the failure mode distribution of the device.     

Temperature modeling and measurement of an electrokinetic separation chip

This work presents experimental [infrared (IR) thermography] and computational (finite element model) results of temperature distributions of an electrokinetic separation chip. Thermal characteristics of both the electrolyte solution and the polymer chip (SU-8) are taken into account in modeling temperature distributions during electrokinetic flow. Multiphysics and multiscale simulation couples electrostatics, heat transfer, and fluid dynamics. The accompanying IR thermography is a non-contact method, which can measure fractional temperature differences with sub-second time resolution. Any structures or temperature marker molecules interfering with the experiment are not needed. Nominal spot size in the IR measurements is 30 μm with a field of view of several millimeters enabling both local and chip-scale temperature monitoring simultaneously. As a result, we present a computer model for electrokinetic chips, which enables simulation of fractional temperature changes during electrophoresis under real operating conditions. The accuracy of the model is within ±1°C when the deviation in electrochemical processes is taken into account. The simulation results also suggest that the temperature on the chip surface qualitatively reflects the temperature inside the microchannel with an average offset of 1–2°C.     

Modelling of transient kinetics in catalytic three-phase reactors: Enantioselective hydrogenation

Transient techniques are frequently used for catalytic gas-phase processes, but the application of transient techniques on catalytic three-phase systems is very scarce. Transient kinetic experiments provide valuable additional information about the behaviour of complex organic reaction systems, which was illustrated here with continuous enantioselective three-phase hydrogenation of ethyl benzoylformate over supported Pt catalyst particles in a fixed bed. The catalyst stability and the details of the adsorption–desorption behaviour of the reaction participants were revealed by transient experiments. Quantitative modelling of the data was based on kinetic experiments and characterisation of the reactor flow pattern by an inert tracer. Both liquid-phase species and adsorbed surface species were included in the modelling. The model predicted correctly the dynamic behaviour of the complex organic system under transient conditions. The approach is generally applicable to complex organic systems undergoing catalytic transformations.