Note: Intro -- UNDERSTANDING MASS SPECTRA Second Edition -- CONTENTS -- Preface to the Second Edition -- Acknowledgments -- Abbreviations and Notations Used in This Book -- 1 Instrumentation -- 1.1. Introduction -- 1.1.1. Overview -- 1.1.2. Sample Introduction -- 1.2. Ionization Source -- 1.2.1. Electron Ionization Source -- 1.2.2. Chemical Ionization -- 1.2.3. Other Ionization Methods -- 1.2.3.1. Electrospray Ionization -- 1.2.3.2. Desorption Ionization -- 1.3. m/z Analysis -- 1.3.1. Time-of-Flight (TOF) -- 1.3.2. Magnetic Sector -- 1.3.3. Transmission Quadrupole -- 1.3.3.1. Selected Ion Monitoring (SIM) -- 1.3.4. Quadrupole Ion Trap (QIT) -- 1.3.5. Other Types of Mass Analysis -- 1.3.5.1. Mass Spectrometry/Mass Spectrometry(MS/MS) -- 1.3.5.2. Accurate m/z Analysis -- 1.3.6. Spectral Skewing -- 1.4. Ion Detection -- 1.4.1. Electron Multiplier -- 1.4.2. Photomultiplier Detector -- 1.5. Data System -- 1.5.1. Instrument Tuning and Calibration -- 1.5.2. The Mass Spectrum -- 1.5.2.1. Production of the Mass Spectrum -- 1.5.2.2. Terminology: Ions vs. Peaks -- 1.5.3. Library Searches -- 1.5.4. Using the Data System to Analyze GC/MS Data -- 1.6. Criteria for Good-Quality Spectra -- Additional Problems -- Mass Spectrometric Resources on the Internet -- References and Suggested Reading -- 2 Elemental Composition from Peak Intensities -- 2.1. Natural Isotopic Abundances -- 2.1.1. Atomic and Molecular Mass -- 2.1.2. Calculated Exact Masses and Mass Defects -- 2.2. Determining Elemental Composition from Isotope Peak Intensities -- 2.2.1. One or More Atoms of a Single Element -- 2.2.1.1. Chlorine and Bromine -- 2.2.1.2. Ion Designation and Nomenclature -- 2.2.1.3. Probability Considerations with Multiple Numbers of Atoms -- 2.2.1.4. Isotope Peak Intensity Ratios for Carbon-Containing Ions-The X + 1 Peak -- 2.2.1.5. A, A + 1, and A + 2 Elements. , 2.2.1.6 Isotope Peak Intensity Ratios for Carbon-Containing Ions-The X + 2 Peak -- 2.2.1.7. Overlapping Peak Clusters-Contributions from (13)C Only -- 2.2.1.8. Silicon -- 2.2.2. Complex Isotope Clusters -- 2.2.2.1. Sulfur Dioxide -- 2.2.2.2. Diazepam -- 2.3. Obtaining Elemental Compositions from Isotope Peak Intensities -- Examples -- Additional Problems -- References -- 3 Ionization, Fragmentation, and Electron Accounting -- 3.1. A Brief Review of Orbitals and Bonding -- 3.2. Even- and Odd-Electron Species -- 3.3. Site of Initial Ionization -- 3.4. Types of Fragmentation -- 3.5. The Nitrogen Rule -- 3.6. Energy Considerations in Fragmentation Processes -- 3.6.1. Fragmentation Rates -- 3.6.2. Metastable Ions -- 3.6.3. Energy Diagrams -- 3.6.4. Stevenson's Rule -- Additional Examples -- Problems -- References -- 4 Neutral Losses and Ion Series -- 4.1. Neutral Losses -- 4.1.1. Losses from the Molecular Ion -- 4.1.2. Loss of Small Molecules from Aromatic Ions -- 4.2. Low-Mass Ion Series -- 4.2.1. n-Alkane Spectra -- 4.2.2. Effect of Chain Branching on the Spectra of Aliphatic Hydrocarbons -- 4.2.3. Ion Series for Nonaromatic Compounds -- 4.2.4. Aromatic Ion Series -- 4.2.5. Use of Ion Series: Mass Chromatograms -- Additional Problems -- References -- 5 A Rational Approach to Mass Spectral Problem Solving -- 5.1. Guidelines for Solving Mass Spectral Problems -- Examples -- Problems -- Reference -- 6 a-Cleavage and Related Fragmentations -- 6.1. Introduction -- 6.2. Benzylic Cleavage -- 6.3. Cleavage Next to Aliphatic Nitrogen -- 6.3.1. Structural Relationships: a-Cleavage in 1-Phenyl-2-aminopropanes -- 6.3.2. Cleavage Next to Electron-Deficient Nitrogen -- 6.3.3. a-Cleavage in Complex Nitrogenous Ring Systems -- 6.4. Cleavages of Aliphatic Oxygenated Compounds -- 6.4.1. a-Cleavage -- 6.4.2. Bond Cleavage Away from the Ionization Site. , 6.4.3. Cleavage at Carbonyl Groups -- 6.5. Elimination Fragmentations in Oxygen and Nitrogen Compounds -- 6.5.1. Secondary Elimination from Initial a-Cleavage Ions -- 6.5.2. Hydride Shifts -- 6.5.3. Elimination Fragmentations of Some Aromatic Compounds -- 6.5.4. Water Elimination in Aliphatic Alcohols -- Examples -- Additional Problems -- References -- 7 Important Mass Spectral Rearrangements -- 7.1. Introduction -- 7.2. g-Hydrogen Rearrangement -- 7.2.1. McLafferty-Type Rearrangement -- 7.2.2. g-Hydrogen Rearrangement in Alkylbenzenes -- 7.2.3. g-Hydrogen Rearrangement Initiated by a Remote Ionization Site -- 7.3. Cyclohexanone-Type Rearrangement -- 7.4. Retro Diels-Alder Fragmentation -- 7.5. Double-Hydrogen (McLafferty + 1) Rearrangement -- Additional Problems -- References -- 8 Rationalizing Mass Spectral Fragmentations -- 8.1. General Guidelines -- 8.2. Loss of Small Molecules -- 8.2.1. Loss of Small Molecules from Aromatic Ions Revisited -- 8.2.2. g-Butyrolactone -- 8.3. Ephedrine -- 8.4. Ortho Effect: The Hydroxybenzoic Acids -- Additional Problems -- References -- 9 Structure Determination in Complex Molecules Using Mass Spectrometry -- 9.1. Introduction -- 9.2. "Designer Drugs" Related to MDA -- 9.3. Cocaine and Its Metabolites -- 9.3.1. Peak Correlations -- 9.3.2. Proposed Fragmentations -- 9.3.3. Application -- 9.4. Phencyclidine and Its Analogs -- 9.4.1. Fragmentations of Phencyclidine -- 9.4.2. Phencyclidine Analogs -- 9.5. A Practical Problem -- References -- 10 Answers to Problems -- Index.