Mobilities of mixtures of ion isotopes in gas mixtures

It is shown how the mobility of a mixture of isotopes of the same ion species in a gas mixture can be obtained directly from mobility data of a single isotope of the ion and one isotope of each neutral species, for any gas temperature and ratio of the electrostatic field strength to the gas number density. This combination of the “aliasing” procedure for ion isotopes, Blanc’s Law for gas mixtures at low fields, and the extended Blanc’s Law at intermediate and high fields is tested by comparing values calculated from the mobilities of ⁷⁹Br^? in ²⁰Ne with those determined both experimentally and ab initio for various mixtures. It is so accurate that it obviates the necessity in future work of making measurements or calculations for more than one isotope of each ion and each neutral.     

Analysis of multicomponent mass spectra applying Bayesian probability theory

In this paper we develop a method for the decomposition of mass spectra of gas mixtures, together with the relevant calibration measurements. The method is based on Bayesian probability theory. Given a set of spectra, the algorithm returns the relative concentrations and the associated margin of confidence for each component of the mixture. In addition to the concentrations, such a data set enables the derivation of improved values of the cracking coefficients of all contributing species, even for those components for which the set does not contain a calibration measurement. This latter feature also allows one to analyze mixtures that contain radicals in addition to stable molecules. As an example, we analyze and discuss the mass spectra obtained from the pyrolysis of azomethane, which contain the radical CH3 apart from nitrogen and C1- and C2-hydrocarbons.     

An implementable approach to obtain reproducible reduced ion mobility

Ion mobility spectrometry is increasingly in demand for medical applications and its potential for implementation in food quality and safety or process control suggest rising use of instruments in this field as well. All those samples are commonly extremely complex and mostly humid mixtures. Therefore, pre-separation techniques have to be applied. As ion mobility spectrometers with gas-chromatographic pre-separation acquire a huge amount of data, effective data processing and automated evaluation by comparison of detected peak pattern with data bases have to be utilised. This requires accurate on-line calibration of the instruments to guarantee reproducible results, in particular with respect to identification of an analyte by determination of its ion mobility and retention time. To reduce environmental and instrumental influence, the reduced ion mobility is used. It is derived from the drift time normalised to electric field, length of the drift region and to temperature and pressure of the drift gas (traditional method). All data required for this normalisation are afflicted with a particular error and thus leading to a deviation of the calculated ion mobility value. Furthermore, this traditional method enables a calculation of the reduced ion mobility only after the measurement. To avoid those errors and to enable on-line calibration of ion mobility, an instrument specific factor is implemented generally representing all relevant variables. This factor can be determined from an initial measurement of few spectra and can thereafter be applied on the following measurement. The application of this approach obtained reproducible reduced ion mobility values for positive and negative ions over a broad drift time range and for common variation of ambient conditions as well for varying instrument conditions such as electric fields respectively drift times and in different drift gases. Moreover, the reduced ion mobility is available already during the measurements with a significantly higher reliability and accuracy which was increased to a factor of 5 compared to the traditional ion mobility determination and enables an on-line identification of analytes for the first time.     

HovaCAL®—a generator for multi-component humid calibration gases

Process control, breath analysis for medical purpose or the investigation of biological samples are new applications of ion mobility spectrometry or differential mobility spectrometry coupled with rapid gas-chromatographic pre-separation. Especially if pre-concentration steps should be avoided, they require a realistic and flexible multi-compound calibration down to the ppt_V range including relative humidity values up to 100% for identification of analytes using mobility and retention time as well as for their quantification using the signal intensity as a measure. With HovaCAL® 3834SP-VOC, a novel calibration gas generator is presented that fulfils those requirements. The performance of HovaCAL® was validated for various compounds and mixtures with varying humidity comparing 3 particular equipments. Excellent results have been obtained with standard deviations of the provided concentrations of <8% and of <0.7% for the relative humidity range of 0–100%. Furthermore, standard deviation of the provided concentrations was <3% for varying experimental conditions. The long term stability of the provided concentrations for different instrumental parameters was proofed, standard deviations of <3% have been obtained. HovaCAL® enables for the first time a reliable calibration with complex humid mixtures down to the ppt_V range and—compared to permeation sources—a flexible and rapid change of compounds.     

Spectrophotometric determination of organic dye mixtures by using multivariate calibration

The simultaneous determination of organic dye mixtures by using spectrophotometric methods is a difficult problem in analytical chemistry, due to spectral interferences. By using multivariate calibration methods such as partial least-squares regression (PLSR), it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration stage. In this study, the calibration model is based on absorption spectra in the 350-650-nm range for a set of 16 different mixtures of reactive red 195, reactive yellow 145 and reactive orange 122 dyes, and made the determination of the dye concentrations possible in a validation set with significantly greater accuracy than the conventional univariate calibration method. By using the developed model it was possible to monitor the decolorization kinetic of one dye (reactive orange 122), when the mixture of the three dyes was previously submitted to an ozonation process.     

Identification of pentacyclic triterpenes by GC-MS-MS

The development of tandem mass spectrometry (MS-MS) and its combination with gas chromatography (GC-MS-MS) has greatly enhanced our ability to analyze exceedingly complex mixtures from a wide variety of sources, including fossil fuels. This paper describes a comparison of the conventional electron impact (El) mass spectral fragmentation patterns, obtained in the MS-MS precursor – product mode, of three oleanane isomers and one ursene, all of which are used as indicators of higher plant input to the sedimentary environment Results show that El and collision-activated dissociation (CAD) spectra are most similar at collision energies between ?15 and ?20 eV.The presence of methyl substituents in these pentacyclic terpenes plays an important role in the process of ring fragmentation: the daughter spectra of the M – 15 fragments can be used to obtain structural information, such as the positions of the double bonds.     

Massenspektrometrische Untersuchungen binärer Mischungen aus Alkalimetall- und Erdalkalimetallhalogeniden

Mass Spectrometrical Investigations of Binary Mixtures Alkali Halide – Alkaline Earth Halide The vapor composition of some binary mixtures alkali halide – alkaline earth halide was investigated by high-temperature mass spectrometry. Concentrations of all molecules in gas phase in dependence on the molar composition of liquid mixture were studied. In the vapors over all mixtures exist gaseous heterocomplexes. With increasing radius of the anion a tendency of decreasing stabilities of 1:1 heterocomplexes is stated. The absolute content of gaseous complexes is a function of the ratio of the vapor pressures of the pure components of mixtures. Calculated formation enthalpies fo various stoichiometric heterocomplexes are given.     

Resolution of complex wax ester mixtures by glass capillary GC

A glass capillary GC method providing high resolution analysis of complex wax ester mixtures is described. The two key parameters needed for evaluating a wax ester mixture for industrial utility – the total carbon chain length and the number of carbon-carbon double bonds present in each component – are simply and rapidly obtained by this method.     

Gas-Chromatographic Analysis of Mixtures of Hydrogen Isotopes

A simple method is proposed for the gas-chromatographic analysis of complex gas mixtures containing hydrogen isotopes; the method is based on the substantial difference in the thermal conductivity of these isotopes. The total peak of the isotopes is recorded in a chromatogram, and the calibration is performed by pure reference gases. The concentrations of impurity gases in the analyzed mixture and in reference samples for each of the hydrogen isotopes are determined simultaneously. The fractional concentrations of protium and deuterium are calculated by the equations involving the heights of the unresolved peaks of hydrogen isotopes in chromatograms and concentrations of impurity components.     

The novel use of gas chromatography-ion mobility-time of flight mass spectrometry with secondary electrospray ionization for complex mixture analysis

Increasing the dimensionality of an analysis enables more detailed and comprehensive investigations of complex mixtures. One dimensional separation techniques like gas chromatography (GC) and ion mobility spectrometry (IMS) provide limited chemical information about complex mixtures. The combination of GC, ion mobility spectrometry, and time-of-flight mass spectrometry (GC-IM-TOFMS) provides three-dimensional separation of complex mixtures. In this work, a hybrid GC-IM-TOFMS with a secondary electrospray ionization (SESI) source provided four types of analytical information: GC retention time, ion mobility drift time, mass-to-charge ratios, and ion intensity. The use of secondary electrospray ionization enables efficient and soft ionization of gaseous sample vapors at atmospheric pressure. Several complex mixtures, including lavender and peppermint essential oils, were analyzed by GC-SESI-IM-TOFMS. The resulting 3D data from these mixtures, each containing greater than 50 components, were plotted as 3D projections. In particular, post-processed data plotted in three dimensions showed that many mass selected GC peaks were resolved into different ion mobility peaks. This technique shows clear promise for further in-depth analyses of complex chemical and biological mixtures.     

Gangliosides' analysis by MALDI-ion mobility MS

The combination of ion mobility with matrix-assisted laser desorption/ionization allows for the rapid separation and analysis of biomolecules in complex mixtures (such as tissue sections and cellular extracts), as isobaric lipid, peptide, and oligonucleotide molecular ions are pre-separated in the mobility cell before mass analysis. In this study, MALDI-IM MS is used to analyze gangliosides, a class of complex glycosphingolipids that has different degrees of sialylation. Both GD1a and GD1b, structural isomers, were studied to see the effects on gas-phase structure depending upon the localization of the sialic acids. A total ganglioside extract from mouse brain was also analyzed to measure the effectiveness of ion mobility to separate out the different ganglioside species in a complex mixture.     

Overtone Mobility Spectrometry: Part 4. OMS-OMS Analyses of Complex Mixtures

A new, two-dimensional overtone mobility spectrometry (OMS-OMS) instrument is described for the analysis of complex peptide mixtures. OMS separations are based on the differences in mobilities of ions in the gas phase. The method utilizes multiple drift regions with modulated drift fields such that only ions with appropriate mobilities are transmitted to the detector. Here we describe a hybrid OMS-OMS combination that utilizes two independently operated OMS regions that are separated by an ion activation region. Mobility-selected ions from the first OMS region are exposed to energizing collisions and may undergo structural transitions before entering the second OMS region. This method generates additional peak capacity and allows for higher selectivity compared with the one-dimensional OMS method. We demonstrate the approach using a three-protein tryptic digest spiked with the peptide Substance P. The [M + 3H]³⁺ ion from Substance P can be completely isolated from other components in this complex mixture prior to introduction into the mass spectrometer.     

气体传感器阵列信号的盲分离研究

本文在使用一个四单元微热板式集成气体传感器阵列测试煤矿中的两种主要易燃易爆气体一氧化碳和甲烷的基础上, 将气体传感器阵列与盲信号分离技术相结合, 讨论了混合气体分析的盲可辨识性, 并使用盲信号分离中的一种主要方法独立分量分析法(ICA)进行了分析和验证.     

Investigation of isomeric flavanol structures in black tea thearubigins using ultraperformance liquid chromatography coupled to hybrid quadrupole/ion mobility/time of flight mass spectrometry

Ultra performance liquid chromatography (UPLC) when coupled to ion mobility (IMS)/orthogonal acceleration time of flight mass spectrometry is a suitable technique for analyzing complex mixtures such as the black tea thearubigins. With the aid of this advanced instrumental analysis, we were able to separate and identify different isomeric components in the complex mixture which could previously not be differentiated by a conventional high performance liquid chromatography/tandem mass spectrometry. In this study, the difference between isomeric structures theasinensins, proanthocyanidins B‐type and rutin (quercetin‐3O‐rutinoside) were studied, and these are present abundantly in many botanical sources. The differentiation between these structures was accomplished according to their acquired mobility drift times differing from the traditional investigations in mass spectrometry, where calculation of theoretical collisional cross sections allowed assignment of the individual isomeric structures. The present work demonstrates UPLC–IMS‐MS as an efficient technology for isolating and separating isobaric and isomeric structures existing in complex mixtures discriminating between them according to their characteristic fragment ions and mobility drift times. Therefore, a rational assignment of isomeric structures in many phenolic secondary metabolites based on the ion mobility data might be useful in mass spectrometry‐based structure analysis in the future. Copyright © 2014 John Wiley & Sons, Ltd.     

First-generation hybrid MEMS gas chromatograph

The fabrication, assembly, and initial testing of a hybrid microfabricated gas chromatograph (microGC) is described. The microGC incorporates capabilities for on-board calibration, sample preconcentration and focused thermal desorption, temperature-programmed separations, and "spectral" detection with an integrated array of microsensors, and is designed for rapid determinations of complex mixtures of environmental contaminants at trace concentrations. Ambient air is used as the carrier gas to avoid the need for on-board gas supplies. The microsystem is plumbed through an etched-Si/glass microfluidic interconnection substrate with fused silica capillaries and employs a miniature commercial pump and valve subsystem for directing sample flow. The latest performance data on each system component are presented followed by first analytical results from the working microsystem. Tradeoffs in system performance as a function of volumetric flow rate are explored. The determination of an 11-vapor mixture of typical indoor air contaminants in less than 90 s is demonstrated with projected detection limits in the low part-per-billion concentration range for a preconcentrated air-sample volume of 0.25 L.     

Multivariate Calibration Transfer between two Potentiometric Multisensor Systems

A multivariate calibration of multisensor systems is a very important stage in their application. Construction of reliable calibration model requires significant investment of time and money. Once established, calibration model can be applied normally only together with that particular multisensor system, which was employed for its’ construction – this can be a serious limitation for a wide adoption of multisensor systems in common laboratory practice. In order to address this issue we have studied the applicability of several calibration transfer techniques, such as direct standardization, single wavelength standardization and standardization with regularization coefficient for the data obtained from two potentiometric multisensor systems in analysis of complex lanthanide mixtures. It was found that mathematical correction of sensor array response using standardization with regularization coefficient allows for using the regression model derived for one sensor array together with the data obtained from another sensor array. The value of root mean squared error of prediction for total lanthanide concentration increased insignificantly (0.10 instead of 0.07 in log scale) compared with that provided by the first multisensor system.     

Theoretical aspects of quantitative mass spectrometry of gas mixtures

The problem of calibration of mass spectrometers with standard gas mixtures is studied theoretically. The results obtained can be used in deciding the number and optimum composition of standard mixtures. An analogy is drawn between this calibration problem and the mathematical theory of experimental design when mixtures are considered. It is shown that calibration based on a number of standard mixtures is more accurate than calibration with pure gases. A procedure for correction of calibration coefficients is described; it can be applied during measurements on the composition of gas mixtures or gas flows. Application to gas mixtures containing CO, N₂ and CO₂ is discussed.     

Mathematical algorithm for qualitative and semiquantitative analysis of petroleum hydrocarbons in solid wastes using on-line gas chromatography

Non-degradated mineral-oils like gasoline, solvent naphtha, diesel fuel, fuel and lubricating oils provide a characteristic fingerprint gas chromatogram. This visual classification, e.g. in solid wastes, is complicated due to the simultaneous presence of several mineral-oils. Therefore, a mathematical algorithm for the separation of gas chromatographic fingerprint of “single mixtures” of aliphatic hydrocarbons is developed. The technique ¶is essential for analysis of time-overlapping “single mixtures” of petroleum hydrocarbons (so-called “complex mixtures”) and it relies on the concentration-varying hydrocarbons during evaporation. It is possible to separate the data from the gas chromatogram of a “complex mixture” of hydrocarbons into the chromatograms of the pure “single mixtures” and to give their respective concentrations. A synthetic ?complex mixture” of kerosene, diesel fuel and lubricating oil is used to illustrate the method.     

Mathematical algorithm for qualitative and semiquantitative analysis of petroleum hydrocarbons in solid wastes using on-line gas chromatography

Non-degradated mineral-oils like gasoline, solvent naphtha, diesel fuel, fuel and lubricating oils provide a characteristic fingerprint gas chromatogram. This visual classification, e.g. in solid wastes, is complicated due to the simultaneous presence of several mineral-oils. Therefore, a mathematical algorithm for the separation of gas chromatographic fingerprint of "single mixtures" of aliphatic hydrocarbons is developed. The technique is essential for analysis of time-overlapping "single mixtures" of petroleum hydrocarbons (so-called "complex mixtures") and it relies on the concentration-varying hydrocarbons during evaporation. It is possible to separate the data from the gas chromatogram of a "complex mixture" of hydrocarbons into the chromatograms of the pure "single mixtures" and to give their respective concentrations. A synthetic "complex mixture" of kerosene, diesel fuel and lubricating oil is used to illustrate the method.     

Phase-titration analysis of ternary mixtures containing mutually miscible components

A method, based on phase-titration, for the analysis of ternary mixtures composed of mutually miscible components is described. One of the components is determined by an independent chemical or physical means and its concentration in the original mixture then brought to a fixed value by adding a calculated amount of one of the three components. The resultant mixture is then titrated to the turbidimetric end-point with a titrant which is immiscible with one of the components and the composition of the sample is computed from a calibration curve. The method is illustrated by its application to benzene-methanol-acetic acid and benzene-toluene-acetic acid mixtures.