Book Description

Overview: The Encyclopedia of Mass Spectrometry The need for an encyclopedia of mass spectrometry (MS) becomes apparent when considering the subject's evolution. By 1990, MS had evolved as a discipline and as a technique for solving problems in chemistry. Along with nuclear magnetic resonance and optical spectroscopy, it was a tool for compound identification. For complex mixtures as found in environmental chemistry, flavors, energy materials, and small-molecule metabolism, gas chromatography-mass spectrometry had become the premier analytical method. Despite these advances, MS played in 1990 only a small role in polar and large-molecule analysis. Field desorption, fast atom bombardment, and Cf-252 plasma desorption gently pushed it into peptide sequencing and molecular weight determination of larger polymers. Although these ionizations had limitations, when they were coupled with tandem mass spectrometers, the future became clearer. MS now awaited the development of new ionization methods that would extend its capabilities into many different research laboratories. The inventions of electrospray ionization (ESI) and matrix-assisted laser desorption ionization (MALDI) in the late 1980s opened the door for that greater role. Even the discipline of MS could expand by embracing the chemical-physical studies of proteins and oligodeoxynucleotides in the gas phase. The broad applicability of MS to a multitude of chemical, physical, and biological problems makes it now the central tool in chemical analysis. No longer a specialist's tool, it has assumed broad applicability and availability. To permit a full and fruitful expansion in other disciplines, the Encyclopedia of Mass Spectrometry is designed to be a learning tool to newcomers who do not have the theoretical and practical background needed to take advantage of the possibilities of MS. Moreover, the field is now so broad that the specialist also needs a resource to allow exploration of its vast reaches. The encyclopedia meets that need and strives to be an entrance into the subject and to serve as its major reference work. Volume 1: Theory and Ion Chemistry Volume 1 begins with two theory chapters. The first discusses theoretical aspects of ion collisions, chemistry, and dynamics, and the second introduces ab initio calculations of ions. The latter has become a nearly indispensable tool in ion chemistry studies today. Instrumentation is essential in fundamental investigations. Chapter 3 introduces instrumentation, with an emphasis on unusual instrumentation, generally not commercially available. Ion traps, ion cyclotron resonance mass spectrometers, and time-of-flight instruments, which are important in both fundamental studies and in applications, are also covered. Chapter 4 discusses myriad means of performing spectroscopic experiments on ions. In the next chapter, various methods of measuring thermodynamic information about ions are introduced and evaluated. Collisional activation and dissociation processes, in various incarnations, are in Chapter 6. Mobility experiments are the focus of the next chapter, which covers fundamental aspects and applications of this rapidly growing technology. Various means and uses of changing charge states of ions is the topic of chapter 8. Chapters 9 and 10 introduce the ion chemistry of organic ions, positive and negative, respectively. The last three chapters (Chapter 11-13) are expositions of the ion chemistry of clusters and solvation phenomena, inorganic chemistry, and the rapidly expanding area of biochemistry. Volume 2: Biological Applications Part A The focus of Volume 2 is peptides and proteins. The organization emphasizes separation techniques, preparation protocols, and fundamentals of ionic gas-phase species of biological importance. This volume is divided into four sections: (1) experimental approaches and protocols, (2) sequence analysis, (3) other structural analyses, and (4) targeted applications. The first section encompass separation procedures (e.g., 2-D gel electrophoresis), sample preparation (e.g., desalting and enzyme digestion), and instrumentation issues (e.g., high resolving power, molecular-weight determination, protein chips, and quantification). H/D exchange, analysis of membrane proteins, and bioinformatics are included. The next section on sequencing covers high energy and low energy CAD, protein identification, fundamentals of peptide fragmentation, bottom-up and top-down strategies, chemical derivatization, and post-source decay with MALDI. A section on structure analysis includes primary structure determination and issues with studying quaternary structure, protein-protein and protein-ligand complexes, disulfide analysis, phosphopeptides and phosphoproteins, selenoproteins, nitrated proteins, metal ion binding, and oxidized proteins. Additional coverage of methods for studying the biophysics of proteins is provided in Volume 6. The last chapter, Targeted Applications, focuses on neuropeptides, clinical applications, enzyme kinetics, imaging, and single-cell analysis. Volume 3: Biological Applications Part B Over the past decades, enormous gains have been made towards the analysis of all the biomolecules in cells. Although early attention was focused on peptides and proteins, a wealth of information is arising about other major biomolecules including nucleic acids, lipids and carbohydrates. In no small way, modern ionization methods, especially electrospray and matrix-assisted laser desorption, have provided a quantum leap in the capabilities of the tools we can now deploy in answering biological questions involving structure and molecular weight of virtually every type of molecule in the cell. Volume 3 covers classes carbohydrates, nucleic acids, and lipids. In addition, special areas of application are also included, such as pharmaceuticals, natural products, isotope ratio methods for biomolecules analysis, and clinical applications. The articles are arranged under general headings for continuity and ease of access, although several of these are of interest across the various disciplines. The articles cover basics and sufficient additional detail to bring the reader up-to-date on a given subject. Some advanced topics are also covered, either in a special section of an article or in additional reading citations. Volume 4: Organic and Organometallic Compounds This volume presents a cross section of applications in organic and organometallic chemistry in two parts. Chapters 1 to 6 are devoted to the fundamentals whereas chapters 7 and 8 cover applications to organic and organometallic compounds, either available as pure compounds or present in complex mixtures. Chapter 1 describes the theory for organic mass spectrometry, building on and complementing material in Volume 1. The themes for Chapter 2 are the structures and properties of gas-phase ions of conventional, distonic, and non-covalent complexes. Chapter 3 covers methodology used in study of gas-phase ions. Chapters 4 and 5 turn to mechanisms of both unimolecular and bimolecular reactions of ions and include topics in stereochemistry and radical chemistry. Chapter 6 contains a number of articles on the formation and reactivity of metal ion complexes and organometallic cations and anions, drawing connections with molecular recognition, catalysis and organic synthesis. Chapter 7 deals with the structure determination of organic compounds, including chiral compounds and natural products. In chapter 8 are contributions that provide illustrative examples of the determination of organic compounds present at low levels in complex samples that originate from various natural and biological sources. Included is an article on the determination of explosives. Volume 5: Elemental and Isotope Ratio Mass Spectrometry This volume focuses on (1) the plethora of mostly atomic ionization techniques that have been coupled to MS for elemental analysis, the measurement of isotope ratios, and even the determination of inorganic compounds and (2) the precise measurement of isotope ratios of organic elements as small gas molecules by isotope ratio mass spectrometry (IRMS). Volume 6: Ionization Methods Volume 6 captures the story of molecular ionization and its phenomenal evolution that makes mass spectrometry the powerful method it is today. Chapters 1 and 2 cover fundamentals and various issues that are common to all ionization (e.g., accurate mass, isotope clusters, and derivatization). Chapters 3-9 acknowledge that some ionization methods are appropriate for gas-phase molecules and others for molecules that are in the solid or liquid states. Chapters 3-6 cover gas-phase molecules, dividing the subject into: (1) ionization of gas-phase molecules by particles (e.g., EI), (2) ionization by photons, (3) ionization by ion-molecule and molecule-molecule reactions (e.g., APCI and DART), and ionization in Strong electric fields (i.e., Electrohydrodynamic and Field Ionization/Desorption). "Ionization in a Strong Electric Field" illustrates the transition to ionization of molecules in the solid or liquid states, covered in Chapters 7-9: (1) spray methods for ionization (e.g., electrospray), (2) desorption ionization by particle bombardment (e.g., FAB), and (3) desorption by photons (e.g., MALDI). Electrospray and MALDI also lead to applications in biophysical chemistry, the theme of Chapter 10. Chapter 11 reconsiders ionization from the view of choosing an ionization method. The range of subjects is from ionization of organic and biomolecules to the study of microorganisms. Volume 7: Mass Analyzers The volume is under preparation Volume 8: Hyphenated Methods Starting with gas chromatography-mass spectrometry (GC-MS) and continuing through GCxGC-MS, LC-MSn, and LC-NMR-MS, hyphenated methods have revolutionized chemical analysis. This volume covers that revolution in two parts. The first (Chapters 1-4) describes principles, instrumentation, and technology, and the second (Chapters 5-10) organizes major application areas in GC-MS and LC-MS. After a general introduction (Chapter 1), attention is paid to principles and instrumentation of GC-MS (Chapter 2) and LC-MS (Chapter 3). Other hyphenated methods, including online combinations of capillary electromigration methods and supercritical fluid chromatography with mass spectrometry, are in Chapter 4. Applications are then covered in the remaining chapters. The application-oriented chapters are focused on the role of mainly LC-MS in the pharmaceutical field (Chapter 5) and biochemical and biotechnological applications (Chapter 10), and the application of both GC-MS and LC-MS in relation to environmental analysis (Chapter 6), food safety and food analysis (Chapter 7), characterization of natural products (Chapter 8), and clinical, toxicological, and forensic analysis (Chapter 9). Volume 9: History of Mass Spectrometry This volume is under preparation. Volume 10: Index * This multi-volume work is the first to provide unparalleled and comprehensive coverage of the full range of topics and techniques * Suitable for new graduate students who are interested but not yet versed in the subject of mass spectrometry * Techniques, methods and applications of mass spectrometry are described in considerable detail; including limitations, current problems, and areas in which the method does not succeed well