Klaus J. Brockmann

Development of a multipurpose ion source for LC-MS and GC-API MS.

Over the past decade, multimode ion sources operating at atmospheric pressure (i.e., more than one ionization method is operative in the ion source enclosure) have received considerable interest. Simultaneous operation of different ionization methods targeting different compound classes within one analysis run has several advantages, including enhanced sample throughput and thus significant laboratory cost reductions. Potential drawbacks are enhanced ion suppression and other undesirable effects of the simultaneous operation of ionization methods. In this contribution we present an alternative approach—the development and characterization of a widely applicable, multipurpose ion source operating at atmospheric pressure. The optimized source geometry allows rapid changing from LC-API methods (ESI, APCI, APLI) to GC-API methods (APCI, APLI, DA-APLI) along with the appropriate coupling of chromatographic equipment required. In addition, true multimode operation of the source is demonstrated for LC-ESI/APLI and LC-APCI/APLI.

Formation of alkyl and hydroxyalkyl hydroperoxides on ozonolysis in water and in air

Abstract Hydroperoxide-specific HPLC was used to determine the yields of alkyl and hydroxyalkyl hydroperoxides in the ozonolysis of ethene, propene, isoprene and α- and β-pinene under two sets of limiting conditions: in dry air and in aqueous solution. Ozonolysis in water (by mixing solutions) gives almost exclusively 1-hydroxyalkyl hydroperoxides, in 10–30% yields, while dry gas-phase ozonolysis gives very little peroxide (below 1%), unless the double bonds have methyl substituents, in which case methyl hydroperoxide is produced (up to 5%). Bubbling ozone through an aqueous solution of propene yields products typical of both the limiting cases.

Combining chip-ESI with APLI (cESILI) as a multimode source for analysis of complex mixtures with ultrahigh-resolution mass spectrometry

Recently we have established atmospheric-pressure laser ionisation (APLI) as a method for coupling time-of-flight mass spectrometric detectors (TOF MS) with chromatographic systems (HPLC and GC) to allow two-photon ionisation of non-polar aromatic compounds. Here we demonstrate that APLI can be combined with chip-electrospray ionisation (cESI) coupled to Fourier-transform-ion cyclotron resonance mass spectrometry (FT-ICR MS) for ultrahigh-resolution analysis of complex samples. With the laser turned off, the analytes are ionised only by ESI, whereas when the laser is switched on non-polar aromatic substances also are ionised. In combination with the extremely high mass resolution of an FT-ICR MS, simultaneous qualitative analysis of polar and non-polar analytes is possible in both positive and negative modes, as is exemplified with a crude oil sample. Nevertheless, ion suppression was observed (up to ca. 70% for D10-pyrene) and thus sample preparation with chromatographic or electrophoretic pre-separation is necessary for quantitative analysis of targets. In addition, for the first time, the dopant-assisted APLI method in combination with cESI (DA-cESILI) was used for determination of 1-nitrocoronene.

The distribution of ion acceptance in atmospheric pressure ion sources: Spatially resolved APLI measurements

It is demonstrated that spatially resolved mass selected analysis using atmospheric pressure laser ionization mass spectrometry (APLI MS) represents a new powerful tool for mechanistic studies of ion-molecule chemistry occurring within atmospheric pressure (AP) ion sources as well as for evaluation and optimization of ion source performance. A focused low-energy UV laser beam is positioned computer controlled orthogonally on a two-dimensional grid in the ion source enclosure. Resonance enhanced multiphoton ionization (REMPI) of selected analytes occurs only within the confined volume of the laser beam. Depending on the experimental conditions and the reactivity of the primary photo-generated ions, specific signal patterns become visible after data treatment, as visualized in, e.g., contour or pseudo-color plots. The resulting spatial dependence of sensitivity is defined in this context as the distribution of ion acceptance (DIA) of the source/analyzer combination. This approach provides a much more detailed analysis of the diverse processes occurring in AP ion sources compared with conventional bulk signal response measurements.

Evidence of neutral radical induced analyte ion transformations in APPI and Near-VUV APLI

We report on the reactions of neutral radical species [OH, Cl, O(3P), H], generated in a typical atmospheric pressure ionization (API) source upon irradiation of the sample gases with either 193 nm laser radiation or 124 nm VUV light, the latter commonly used in atmospheric pressure photoionization (APPI). The present investigations focus on the polycyclic aromatic hydrocarbon pyrene as representative of the aromatic compound class. Experimental results are supported by computational methods: simple kinetic models are used to estimate the temporal evolution of the concentrations of reactants, intermediates, and final products, whereas density functional theory (DFT) energy calculations are carried out to further elucidate the proposed reaction pathways. The neutral radicals are generated upon photolysis of background water and oxygen always present in appreciable mixing ratios in typical API sources. Substantial amounts of oxygenated analyte product ions are observed using both techniques. In contrast, upon atmospheric pressure laser ionization (APLI) with 248 nm radiation, oxygenated products are virtually absent. In addition, kinetic data evaluation yielded a bimolecular rate constant of k=(1.9±0.9)×10−9 cm3 molecule−1 s−1 for the reaction of the pyrene radical cation with OH radicals.

Are Clusters Important in Understanding the Mechanisms in Atmospheric Pressure Ionization? Part 1: Reagent Ion Generation and Chemical Control of Ion Populations

AbstractIt is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region. Figureᅟ

Numerical Simulation and Experimental Validation of the Three-Dimensional Flow Field and Relative Analyte Concentration Distribution in an Atmospheric Pressure Ion Source

In this study, the validation and analysis of steady state numerical simulations of the gas flows within a multi-purpose ion source (MPIS) are presented. The experimental results were obtained with particle image velocimetry (PIV) measurements in a non-scaled MPIS. Two-dimensional time-averaged velocity and turbulent kinetic energy distributions are presented for two dry gas volume flow rates. The numerical results of the validation simulations are in very good agreement with the experimental data. All significant flow features have been correctly predicted within the accuracy of the experiments. For technical reasons, the experiments were conducted at room temperature. Thus, numerical simulations of ionization conditions at two operating points of the MPIS are also presented. It is clearly shown that the dry gas volume flow rate has the most significant impact on the overall flow pattern within the APLI source; far less critical is the (larger) nebulization gas flow. In addition to the approximate solution of Reynolds-Averaged Navier-Stokes equations, a transport equation for the relative analyte concentration has been solved. The results yield information on the three-dimensional analyte distribution within the source. It becomes evident that for ion transport into the MS ion transfer capillary, electromagnetic forces are at least as important as fluid dynamic forces. However, only the fluid dynamics determines the three-dimensional distribution of analyte gas. Thus, local flow phenomena in close proximity to the spray shield are strongly impacting on the ionization efficiency.

Gas Flow Dynamics in Inlet Capillaries: Evidence for non Laminar Conditions

AbstractIn this work, the characteristics of gas flow in inlet capillaries are examined. Such inlet capillaries are widely used as a first flow restriction stage in commercial atmospheric pressure ionization mass spectrometers. Contrary to the common assumption, we consider the gas flow in typical glass inlet capillaries with 0.5 to 0.6 mm inner diameters and lengths about 20 cm as transitional or turbulent. The measured volume flow of the choked turbulent gas stream in such capillaries is 0.8 L·min−1 to 1.6 L·min−1 under typical operation conditions, which is in good agreement to theoretically calculated values. Likewise, the change of the volume flow in dependence of the pressure difference along the capillary agrees well with a theoretical model for turbulent conditions as well as with exemplary measurements of the static pressure inside the capillary channel. However, the results for the volume flow of heated glass and metal inlet capillaries are neither in agreement with turbulent nor with laminar models. The velocity profile of the neutral gas in a quartz capillary with an inner diameter similar to commercial inlet capillaries was experimentally determined with spatially resolved ion transfer time measurements. The determined gas velocity profiles do not contradict the turbulent character of the flow. Finally, inducing disturbances of the gas flow by placing obstacles in the capillary channel is found to not change the flow characteristics significantly. In combination the findings suggest that laminar conditions inside inlet capillaries are not a valid primary explanation for the observed high ion transparency of inlet capillaries under common operation conditions. Graphical Abstractᅟ

Capillary Atmospheric Pressure Electron Capture Ionization (cAPECI): A Highly Efficient Ionization Method for Nitroaromatic Compounds

AbstractWe report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2– or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2– leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry. Figureᅟ

Design Study of an Atmospheric Pressure Photoionization Interface for GC-MS

AbstractThis contribution reports on the development of an atmospheric pressure photoionization (APPI) source interfacing a gas chromatograph (GC) with a bench-top Orbitrap high resolution mass spectrometer (MS). We present efforts on method development aiming at high temperature stability (325°C), constant low impurity levels upon prolonged source operation, and efficient reaction volume irradiation combined with minimum peak broadening. The performance throughout each iterative development step was carefully assessed. The final GC-APPI-MS setup demonstrated femtogram-on-column sensitivity and chromatographic peaks of Gaussian shape with base peak widths <2 s for even the highest boiling compounds present in different EPA standard mixtures. Graphical Abstractᅟ