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JГјrgen H Gross - Mass Spectrometry

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JГјrgen H Gross Mass Spectrometry
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Springer International Publishing AG 2017
Jrgen H Gross Mass Spectrometry 10.1007/978-3-319-54398-7_1
1. Introduction
Jrgen H. Gross 1
(1)
Institute of Organic Chemistry, Heidelberg University, Heidelberg, Germany
Learning Objectives
  • The relevance of mass spectrometry
  • Mass spectrometry Basic concepts
  • How mass spectra are displayed and communicated
  • The performance features of mass spectrometry
  • Basic terminology and conventions in data presentation
  • Aims and scope and general organization of this textbook
1.1 Mass Spectrometry: Versatile and Indispensable
Mass spectrometry (MS) is an indispensable analytical tool in chemistry, biochemistry, pharmacy, medicine, and many related fields of science. No student, researcher or practitioner in these disciplines can really get by without a substantial knowledge of mass spectrometry.
Structure elucidation of unknown substances, environmental and forensic analytes, quality control of drugs, foods, and polymers all rely to a great extent on mass spectrometry [].
Whatever the analytical interest may be: mass spectrometry aims to identify a compound from the molecular or atomic mass(es) of its constituents. The information delivered by mass alone can be sufficient for the identification of elements and the determination of the molecular formula of an analyte. The relative abundance of isotopologs helps to decide which elements contribute to such a formula and to estimate the number of atoms of a contributing element. Under the conditions of certain mass spectrometric experiments, fragmentation of ions can deliver information on ionic structure. Thus, MS elucidates the connectivity of atoms within smaller molecules, identifies functional groups, determines the (average) number and eventually the sequence of constituents of macromolecules, and in some cases even yields their three-dimensional structure (Table ).
Table 1.1
Fields of application of mass spectrometry
Key application and field of application
Explanation
Elemental and isotopic analysis
Physics
Radiochemistry
Geochemistry
Elemental identification and isotopic abundance measurement of both short-lived and stable species in physics and radiochemistry (nuclear waste), in geochemistry and more recently in the life sciences.
Organic and bio-organic analysis
Organic chemistry
Polymer chemistry
Biochemistry and medicine
Identification and structural characterization of molecules from small to very large as provided either by chemistry, physiological processes, or polymer chemistry.
Structure elucidation
Organic chemistry
Polymer chemistry
Biochemistry and medicine
Mass spectrometric experiments can be arranged consecutively to study mass-selected ions in tandem mass spectrometry (MS/MS or MS2). Eventually products are subjected to a third level (MS3) and so forth (MSn).
Characterization of ionic species and chemical reactions
Physical chemistry
Thermochemistry
Tandem MS provides an elegant means for the study of unimolecular or bimolecular reactions of gas phase ions and for the determination of ion energetics.
Coupling to separation techniques
Quality control
Environmental analysis
Complex mixture analysis
Forensics
Petroleum chemistry
Food chemistry
MS can be coupled to separation methods such as gas chromatography (GC) and liquid chromatography (LC). In hyphenation, i.e., as GC-MS or LC-MS, MS delivers high selectivity and low detection limits for the analysis of trace compounds in complicated matrices or the deconvolution of complex mixtures.
Mass spectral imaging
Biomedical studies
Pharmaceutical developments
Material sciences
Mass spectra can be obtained from micrometer-sized areas on surfaces, translating the lateral distribution of compounds on surfaces (microelectronics, slices of tissue) into images, which in turn can be correlated to optical images.
Miniaturization
Field portable MS
Space missions
Military applications
Mass spectrometers can be very small. Portable instruments allow for environmental on-site analysis, detection systems for explosives and warfare chemicals, and last but not least for many space missions.
1.2 Historical Sketch
1.2.1 The First Mass Spectra
The first instrument to separate ions by mass-to-charge ratio was constructed by Joseph John Thomson (Nobel Prize in physics in 1906 for the discovery of the electron) in his attempt to understand electric discharges in gases and to analyze the charged gas phase species involved. His work [). While Thomsons original book from 1913 is hard to come by, there is a reprint by the American Society for Mass Spectrometry (ASMS) that is readily available.
Fig 11 The Thomson Medal in honor of Joseph John Thomson generally regarded - photo 1
Fig. 1.1
The Thomson Medal in honor of Joseph John Thomson, generally regarded as the father of mass spectrometry, is awarded by the International Mass Spectrometry Foundation (IMSS) to outstanding scientists in the field of mass spectrometry
Particularly due to Francis William Astons work in the following decade, the new revolutionary technique soon provided means for the atomic characterization of numerous elements []. Further Nobel Prizes related to MS are tabulated in the Appendix.
1.2.2 Thomsons Parabola Spectrograph
Thomsons apparatus, the parabola spectrograph , employs parallel magnetic and electric fields to achieve a deflection of ionic species depending on charge sign, charge, and mass. Ions exiting the ion source are passed through a collimator to create a roughly parallel beam that is then sent into the analyzer (Fig..)
Fig 12 Parabola spectrograph as constructed by J J Thomson a - photo 2
Fig. 1.2
Parabola spectrograph as constructed by J. J. Thomson. ( a ) Schematic, ( b ) photograph of the light emission from the fluorescent screen as obtained with this instrument (shown rotated by 90 with respect to the schematic) (Adapted from Ref. [] with kind permission of Curt Brunne)
1.2.3 Milestones
Thomson and Aston only marked the beginnings of what expanded into more than a century of exciting developments in mass spectrometry, the major milestones of which were recently compiled [].
The pioneering mass spectrometrist worked with home-built rather than commercial instruments. These machines, typically magnetic sector instruments using electron ionization, delivered a few mass spectra per day, providing that the device was delicately handled. Intimate knowledge of such an instrument and interpretation skills of the according EI spectra would provide the mass spectrometrist with a previously unknown wealth of insight into structural details []. The life sciences, in particular, have provided a great impetus for new developments that expand the mass range to higher molecular weights and increasingly fragile molecules. Environmental and pharmaceutical research has been a driving force in reaching even lower limits of detection. Current research is aimed at methods of ion sampling, ion generation, and subsequent ion transfer into mass analyzers for superior performance.
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