19 research outputs found
Recommendations for reporting ion mobility mass spectrometry measurements
© 2019 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc. Here we present a guide to ion mobility mass spectrometry experiments, which covers both linear and nonlinear methods: what is measured, how the measurements are done, and how to report the results, including the uncertainties of mobility and collision cross section values. The guide aims to clarify some possibly confusing concepts, and the reporting recommendations should help researchers, authors and reviewers to contribute comprehensive reports, so that the ion mobility data can be reused more confidently. Starting from the concept of the definition of the measurand, we emphasize that (i) mobility values (K0) depend intrinsically on ion structure, the nature of the bath gas, temperature, and E/N; (ii) ion mobility does not measure molecular surfaces directly, but collision cross section (CCS) values are derived from mobility values using a physical model; (iii) methods relying on calibration are empirical (and thus may provide method-dependent results) only if the gas nature, temperature or E/N cannot match those of the primary method. Our analysis highlights the urgency of a community effort toward establishing primary standards and reference materials for ion mobility, and provides recommendations to do so. © 2019 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc
Using sheath-liquid reagents for capillary electrophoresis-mass spectrometry: Application to the analysis of phenolic plant extracts
The combination of CE and MS is now a widely used tool that can provide a combination of high resolution separations with detailed structural information. Recently, we highlighted the benefits of an approach to add further functionality to this well-established hyphenated technique, namely the possibility to perform chemical reactions within the sheath-liquid of the CE-MS interface . Apart from using hydrogen/deuterium exchange for online determination of numbers of exchangeable protons, the addition of DPPH• (2,2-diphenyl-1-picrylhydrazyl) to the sheath-liquid can be used as a fast screening tool for studying antioxidant characteristics of individual components. Such a CE-MS methodology allows rapid and information-rich analysis with minimal reagent and sample consumption to be performed. In the present work, we demonstrate the applicability of this approach for the characterization of phenolic plant extracts from the Labiatae family, namely Rosmarinus officinalis and Melissa officinalis. Using the described approach, a wide range of compounds (15 and 13 phenolic compounds, respectively) could be confidently identified using a combination of high resolution CE-MS separations with implementation of online deuterium exchange and DPPH• reactions. These compounds included polyphenols, phenolic acids, and triterpene acids. In conjunction with online MS/MS experiments, extensive structural information for aglyconic and glycosylated antioxidants present in the extracts could be obtained using simple experimental changes, which can be carried out prior to the purchasing of expensive chemical standards or the time-consuming preparative isolation of individual compounds.T.J.C. is the recipient of a Lise Meitner Fellowship (M1572-N19) from the Austrian Science Funds (FWF).Peer Reviewe
High temperature liquid chromatography with monolithic capillary columns and pure water eluent
Temperature pulsing for controlling chromatographic resolution in capillary liquid chromatography
Molecular Weight and Tacticity of Oligoacrylates by Capillary Electrophoresis-Mass Spectrometry
International audienceOligo(acrylic acid) efficiently stabilizes polymeric particles, especially particles produced by reversible addition-fragmentation chain transfer (RAFT) (as hydrophilic block of an amphiphilic copolymer). Capillary electrophoresis (CE) has a far higher resolution power to separate these oligomers than the commonly used size exclusion chromatography. Coupling CE to electrospray ionization mass spectrometric detection unravels the separation mechanism. CE separates these oligomers, not only according to their degree of polymerization, but also according to their tacticity, in agreement with NMR analysis. Such analysis will provide insight into the role of these oligomers as stabilizers in emulsion polymerization, and into the mechanism of the RAFT polymerization with respect to degree of polymerization and tacticity
Probing the kinetic performance limits for ion chromatography. II. Gradient conditions for small ions
Plate-height model of ion mobility-mass spectrometry
In the past decade, ion mobility spectrometry (IMS) in combination with mass spectrometry (IM-MS) became a widely employed technique for the separation and structural characterization of ionic species in the gas phase. Similarly to chromatography, where studies on the mechanism of band broadening and adequate plate-height equations have been aiding method development and promoting advancements in column technology, a suitable resolving power theory of drift tube ion mobility-mass spectrometry (DTIM-MS) is essential to stimulate further progress in this emerging field of separation science. In the present study, therefore, we explore dispersion processes in detail and present a plate-height model of ion mobility-mass spectrometry. We quantify the effects of five major dispersion processes that contribute to zone broadening and determine the resolving power in DTIM-MS: diffusion, Coulomb repulsion, electric field inhomogeneities, the finite initial spread of the ion cloud and dispersion outside the mobility cell. A solution is provided to account for the nonuniform separation field in IM-MS in the presence of multiple compartments. The equations - derived from first principles - serve as the basis for formulating an expression that is similar in nature to van Deemter's plate-height equation for chromatography. A comprehensive set of experiments was performed on a custom-built DTIM-MS instrument to evaluate the accuracy of the plate-height model, resulting in satisfactory agreement between experiment and theory. Building on these findings, the plate-height equation was employed to explore the influence of drift gas pressure, injection pulse-width and the mobility of ions on resolving power from a theoretical point of view. Our findings may aid instrument design and development in the future, as well as the optimization of measurement conditions to improve ion mobility separations. By employing the plate-height concept and the general formalism of differential migration processes to describe zone spreading in IM-MS, we aim to find a common ground between this emerging method and such well-established techniques as HPLC or CZE. We also hope that the work presented here will facilitate a broader acceptance of IMS as a separation method of great potential by the communities of chromatography and electrophoresis, as well as that of mass spectrometry
Plate-height model of ion mobility-mass spectrometry: Part 2—Peak-to-peak resolution and peak capacity
In a previous work, we explored zone broadening and the achievable plate numbers in linear drift tube ion mobility-mass spectrometry through developing a plate-height model [1]. On the basis of these findings, the present theoretical study extends the model by exploring peak-to-peak resolution and peak capacity in ion mobility separations. The first part provides a critical overview of chromatography-influenced resolution equations, including refinement of existing formulae. Furthermore, we present exact resolution equations for drift tube ion mobility spectrometry based on first principles. Upon implementing simple modifications, these exact formulae could be readily extended to traveling wave ion mobility separations and to cases when ion mobility spectrometry is coupled to mass spectrometry. The second part focuses on peak capacity. The well-known assumptions of constant plate number and constant peak width form the basis of existing approximate solutions. To overcome their limitations, an exact peak capacity equation is derived for drift tube ion mobility spectrometry. This exact solution is rooted in a suitable physical model of peak broadening, accounting for the finite injection pulse and subsequent diffusional spreading. By borrowing concepts from the theoretical toolbox of chromatography, we believe that the present study will help in integrating ion mobility spectrometry into the unified language of separation science
Temperature Pulsing for Controlling Chromatographic Resolution in Capillary Liquid Chromatography
In this study we introduce the implementation of rapid
temperature
pulses for selectivity tuning in capillary liquid chromatography.
Short temperature pulses improved resolution in discrete sections
of chromatograms, demonstrated for ion-exchange chromatography (IC)
and hydrophilic interaction chromatography (HILIC) modes. Using a
resistively heated column module capable of accurate and rapid temperature
changes, this concept is first illustrated with separations of small
anions by IC using a packed capillary column as well as a series of
nucleobases and nucleosides by HILIC using a silica monolithic column
with zwitterionic functionality (ZIC-HILIC). Both positive (increasing
temperature) and negative temperature pulses are demonstrated to produce
significant changes in selectivity and are useful approaches for improving
resolution between coeluted compounds. The approach was shown to be
reproducible over a large number of replicates. Finally, the use of
temperature gradients as well as other complex temperature profiles
was also examined for both IC and HILIC separations
Assessing the Nanoscale Structure and Mechanical Properties of Polymer Monoliths used for Chromatography
Concerning
polymeric monolithic materials utilized in separation
science, the structural and mechanical characteristics from the nanoscopic
to the macroscopic scale remain of great interest. Suitable analytical
tools are urgently required to understand the polymer monolith’s
constituent structure, particularly in the case of nanoscale polymer
properties that tend to develop gel porosity in contact with a mobile
phase ultimately affecting the chromatographic performance. Herein
described are our first findings from a characterization of commercially
available analytical polymer monoliths based on styrene/divinylbenzene
and methacrylate chemistries utilizing confocal Raman spectroscopy
imaging and atomic force microscopy (AFM). Confocal Raman spectroscopy
can be used to generate a three-dimensional representation of monoliths
in both dry state and in contact with solvent. AFM force–indentation
measurements on individual cross-sectioned globular features permit
detailed assessment of mechanical properties of the stationary phase.
This approach allowed so far unprecedented insight and identification
of a heterogeneous cross-link density distribution of polymer material
within individual globular features on a submicrometer scale