Laser Ionization Mass Analysis

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1 Laser Ionization Mass Analysis Edited by AKOS VERTES George Washington University Washington, D.C. RENAAT GIJBELS FRED ADAMS University of Antwerp (UIA) Antwerp, Belgium A WILEY-INTERSCIENCE PUBLICATION JOHN WILEY & SONS, INC. New York / Chichester / Brisbane / Toronto / Singapore

2 CONTRIBUTORS FOREWORD CUMULATIVE LISTING OF VOLUMES IN SERIES CHAPTER 1 INTRODUCTION Akos Vertes, Renaat Gijbels, and Fred Adams References XUI XV xvü CHAPTER 2 LASERS IN MASS SPECTROMETRY: ORGANIC AND INORGANIC INSTRUMENTATION 7 Luc Van Vaeck, Wim Van Roy, Renaat Gijbels, and Fred Adams 2.1. Introduction Early Applications in Elemental Analysis of Solids Early Applications in Organic Mass Spectrometry Magnetic Sector LD-MS Instruments Quadrupole LD-MS Instruments Time-of-Flight LD-MS Instruments LD in FTMS Instruments Ion Storage LD-MS Instruments Laser Microprobe Mass Spectrometry (LMMS) Laser Probe Mass Spectrograph (LPMS) Laser Microprobe with TOF-MS Laser Microprobe with FTMS Laser Ablation in Two-Step Desorption and Ionization Inorganic Applications 55 v

3 Organic Applications Laser Desorption and Nonlaser Postionization Inorganic Applications Organic Applications Laser Desorption and Ionization in a Two-Step Process Inorganic Applications Organic Applications Lasers at Other Stages of the MS Experiment Multistage Experiments in Magnetic Sector MS Multistage Experiments in TOF-MS Multistage Experiments in Quadrupole Ion Trap MS Multistage Experiments in FTMS 107 List of Acronyms 115 References 116 METHODS UTILIZING LOW AND MEDIUM LASER IRRADIANCE Laser-Induced Thermal Desorption and Matrix- Assisted Methods 127 Akos Vertes and Renaat Gijbels 3A.1. Introduction 127 3A.2. Laser-Induced Thermal Desorption 130 3A.3. The Irradiance Threshold for Plume Formation 132 3A.4. Matrix-Assisted Laser Desorption 135 3A.5. MALD in the Analysis of Biological Molecules 141 3A.5.1. Peptides and Polypeptides 141 3A.5.2. Proteins 143 3A.5.3. Nucleotides 147 3A.5.4. Carbohydrates 148 3A.5.5. Other Compounds 149 3A.6. Proposed Mechanisms and Models 152 3A.6.1. Phase Explosion 153 3A.6.2. The Cool Plume Model 154

4 Vll 3A.6.3. Desorption Induced by Electronic Transition 158 3A.6.4. The Pressure Pulse Model 160 3A.6.5. Energy Redistribution Processes 162 3A.7. Ion Formation 167 References 169 B. Structural Characterization of Organic Molecules by Laser Mass Spectrometry 177 Luc Van Vaeck, Wim Van Roy, Renaat Gijbels, and Fred Adams 3B.1. 3B.2. 3B.3. Introduction Some General Concepts in LD-MS 3B.2.1. Thermal Ionization and Generation of Neutrais in LD-MS 3B.2.2. Gas Phase Ion-Molecule Reactions in LD-MS 3B.2.3. Shockwave or Nonthermal Desorption in LD-MS 3B.2.4. Resonant Desorption in LD-MS 3B.2.5. Ionization in TOF-LMMS Survey of LD Mass Spectra for Diagnostic Analysis 3B B B B B B B B B B B Polycylic Aromatic Hydrocarbons (PAHs) and Related Analogues Simple Molecules Medium-Sized Polyfunctional Molecules Oligosaccharides Nucleosides and Nucleotides Glycosides Amino Acids Oligopeptides Lipopolysaccharides Polymers Ionic Compounds and Salts 3B.4. Local Analysis by Means of Structural Ions References

5 Vlll Two-Step Methods for Separated Volatilization and Laser-Induced Multiphoton Ionization of Small Biological Molecules in Supersonic Jets 321 David M. Lubman 3C.1. 3C.2. 3C.3. 3C.4. 3C.5. References Introduction Principles of Resonance-Enhanced Multiphoton Ionization Experimental Methodology 3C.3.1. Apparatus 3C.3.2. Desorption Method 3C.3.3. Supersonic Jet Cooling 3C.3.4. Laser Ionization Applications 3C.4.1. Spectroscopy and Mass Spectrometry of Neurotransmitters and Other Small Biological Molecules 3C.4.2. Mass Spectrometry and Spectroscopy of Peptides Conclusions CHAPTER 4 THE HIGH LASER IRRADIANCE REGIME A. Laser Ablation and Plasma Formation 369 Claude R. Phipps and Russell W. Dreyfus 4A.1. Plasma-Mediated Laser-Target Coupling at Irradiance Greater than 1 GW/cm A.1.1. Introduction 369 4A.1.2. Basic Concepts: Survey of the Four Interaction Regions 372 4A.1.3. Applicability Conditions for High- Irradiance Theory 377 4A.1.4. High-Irradiance Absorption and Ignition at the Solid Surface 381 4A.1.5. Absorption and Energy Redistribution Processes in Dense LTE Plasma

6 IX 4A.1.6. What Can Be Learned About Ablation Parameters from a General Theory? 396 4A.2. Experimental Results for High Irradiance 407 4A.2.1. Mass Loss Rate 407 4A.2.2. Ablation Depth 408 4A.3. Ion Acceleration in the Low-Density Plume 411 4A.3.1. Experiments 411 4A.3.2. Theory and Modeling 415 4A.4. Measurement Techniques in the Low-Density Plume Created by High Laser Irradiance 420 4A.4.1. Langmuir Probes 420 4A.4.2. TimeofFlight 422 4A.4.3. Laser-Induced Fluorescence 423 4A.4.4. Other Ion Diagnostics 424 4A.5. Summary and Conclusions 426 References 426 B. Solid Sampling for Analysis by Laser Ablation 433 Lieselotte Moenke-Blankenburg 4B.1. Introduction 433 4B.2. Microplume Generation 434 4B.2.1. Laser 435 4B.2.2. Laser-Target Interaction 435 4B.3. Laser Microprobe Mass Spectrometry (LMMS) 437 4B.4. Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) 440 4B.5. Conclusions 450 References 450

7 C. Inorganic Trace Analysis by Laser-Induced Mass Spectrometry 453 Hans-Joachim Dietze and Johanna Sabine Becker 4C.1. Introduction 4C.2. Laser Mass Spectrometric Techniques for Inorganic Trace Analysis 4C.2.1. Laser Ionization Mass Spectrometry (LIMS) 4C.2.2. Resonance Ionization Mass Spectrometry (RIMS) 4C.2.3. Laser Ablation Mass Spectrometry (LAMS) 4C.3. Instrumentation and Experimental Conditions 4C.4. Analytical Features 4C.4.1. Fundamentals 4C.4.2. Detection Limits, Sensitivity, Precision, and Accuracy 4C.4.3. Appearance of Molecular and Cluster Ions in Laser-Inducd Mass Spectra 4C.5. Applications of Laser-Induced Mass Spectrometric Methods 4C.5.1. Application to Metals 4C.5.2. Application to Semiconductors and Insulators 4C.5.3. Geological Applications 4C.5.4. Applications of RIMS 4C.5.5. Application to Depth Profiling and Local Analysis 4C.6. Conclusion References

8 XI CHAPTER 5 EXOTIC INSTRUMENTS AND APPLICATIONS OF LASER IONIZATION MASS SPECTROMETRY IN SPACE RESEARCH 505 George G. Managadze and Igor Yu. Shutyaev 5.1. Introduction LIMA-D: A Remote Laser Mass Analyzer for Space Applications General Description of LIMA-D and the History of Its Design The Reflector: Calculations and Construction The Laser and Focusing System Control and On-Board Data Processing Laboratory Experiments with LIMA-D and In-Flight Tests A Promising Instrument for the Future Asteroid Mission LASMA: A Miniature Laser Mass Analyzer Description of the Instrument Test Results: Resolution, Sensitivity, and Accuracy of Analysis Applications of Mini-MS: Advantages and Disadvantages Perspectives of Mini-MS Design in Our Laboratory 544 Note Added in Proof 545 References 547 INDEX 551

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