Mass Spectrometry in Polymer Chemistry -- Contents -- List of Contributors -- Introduction -- 1 Mass Analysis -- 1.1 Introduction -- 1.2 Measures of Performance -- 1.2.1 Mass Resolving Power -- 1.2.2 Mass Accuracy -- 1.2.3 Mass Range -- 1.2.4 Linear Dynamic Range -- 1.2.5 Abundance Sensitivity -- 1.3 Instrumentation -- 1.3.1 Sector Mass Analyzers -- 1.3.2 Quadrupole Mass Filters -- 1.3.3 3D Ion Traps -- 1.3.4 Linear Ion Traps -- 1.3.5 Time-of-Flight Mass Analyzers -- 1.3.6 Fourier Transform Ion Cyclotron Resonance Mass Analyzers -- 1.3.7 Orbitraps -- 1.4 Instrumentation in Tandem and Multiple-Stage Mass Spectrometry -- 1.5 Conclusions and Outlook -- References -- 2 Ionization Techniques for Polymer Mass Spectrometry -- 2.1 Introduction -- 2.2 Small Molecule Ionization Era -- 2.2.1 Electron Ionization (EI) -- 2.2.2 Chemical Ionization (CI) -- 2.2.3 Pyrolysis Mass Spectrometry (Py-MS) -- 2.3 Macromass Era of Ionization -- 2.3.1 Field Desorption (FD) and Field Ionization (FI) -- 2.3.2 Secondary Ion Mass Spectrometry (SIMS) -- 2.3.3 Fast Atom Bombardment (FAB) and Liquid Secondary Ion Mass Spectrometry (LSIMS) -- 2.3.4 Laser Desorption (LD) -- 2.3.5 Plasma Desorption (PD) -- 2.3.6 Other Ionization Methods -- 2.4 Modern Era of Ionization Techniques -- 2.4.1 Electrospray Ionization (ESI) -- 2.4.2 New Trends -- 2.4.3 Atmospheric Pressure Chemical Ionization (APCI) -- 2.4.4 New Trends -- 2.4.5 Matrix-Assisted Laser Desorption/Ionization (MALDI) -- 2.4.6 New Trends -- 2.5 Conclusions -- References -- 3 Tandem Mass Spectrometry Analysis of Polymer Structures and Architectures -- 3.1 Introduction -- 3.2 Activation Methods -- 3.2.1 Collisionally Activated Dissociation (CAD) -- 3.2.2 Surface-Induced Dissociation (SID) -- 3.2.3 Photodissociation Methods -- 3.2.4 Electron Capture Dissociation and Electron Transfer Dissociation (ECD/ETD).

3.2.5 Post-Source Decay (PSD) -- 3.3 Instrumentation -- 3.3.1 Quadrupole Ion Trap (QIT) Mass Spectrometers -- 3.3.2 Quadrupole/time-of-flight (Q/ToF) Mass Spectrometers -- 3.3.3 ToF/ToF Instruments -- 3.4 Structural Information from MS2 Studies -- 3.4.1 End-Group Analysis and Isomer/Isobar Differentiation -- 3.4.2 Polymer Architectures -- 3.4.3 Copolymer Sequences -- 3.4.4 Assessment of Intrinsic Stabilities and Binding Energies -- 3.5 Summary and Outlook -- References -- 4 Matrix-Assisted Inlet Ionization and Solvent-Free Gas-Phase Separation Using Ion Mobility Spectrometry for Imaging and Electron Transfer Dissociation Mass Spectrometry of Polymers -- 4.1 Overview -- 4.2 Introduction -- 4.3 New Sample Introduction Technologies -- 4.3.1 Laserspray Ionization - Ion Mobility Spectrometry-Mass Spectrometry -- 4.3.2 Matrix Assisted Inlet Ionization (MAII) -- 4.3.3 LSIV in Reflection Geometry at Intermediate Pressure (IP) -- 4.4 Fragmentation by ETD and CID -- 4.5 Surface Analyses by Imaging MS -- 4.5.1 Ultraf Fast LSII-MS Imaging in Transmission Geometry (TG) -- 4.5.2 LSIV-IMS-MS Imaging in Reflection Geometry (RG) -- 4.6 Future Outlook -- References -- 5 Polymer MALDI Sample Preparation -- 5.1 Introduction -- 5.2 Roles of the Matrix -- 5.2.1 Intimate Contact -- 5.2.2 Absorption of Laser Light -- 5.2.3 Efficient Desorption -- 5.2.4 Effective Ionization -- 5.3 Choice of Matrix -- 5.4 Choice of the Solvent -- 5.5 Basic Solvent-Based Sample Preparation Recipe -- 5.6 Deposition Methods -- 5.7 Solvent-Free Sample Preparation -- 5.8 The Vortex Method -- 5.9 Matrix-to-Analyte Ratio -- 5.10 Salt-to-Analyte Ratio -- 5.11 Chromatography as Sample Preparation -- 5.12 Problems in MALDI Sample Preparation -- 5.13 Predicting MALDI Sample Preparation -- 5.14 Conclusions -- References -- 6 Surface Analysis and Imaging Techniques -- 6.1 Imaging Mass Spectrometry.

6.2 Secondary Ion Mass Spectrometry -- 6.2.1 Static SIMS of Polymers -- 6.2.1.1 The Fingerprint Region -- 6.2.1.2 High-Mass Region -- 6.2.2 Imaging in Polymer Blends and Multicomponent Systems -- 6.2.3 Data Analysis Methods -- 6.2.4 Polymer Depth Profiling with Cluster Ion Beams -- 6.2.4.1 A Brief Discussion on the Physics and Chemistry of Sputtering and its Role in Optimized Beam Conditions -- 6.2.5 3-D Analysis in Polymer Systems -- 6.3 Matrix-Assisted Laser Desorption Ionization (MALDI) -- 6.3.1 History of MALDI Imaging Mass Spectrometry -- 6.3.2 Sample Preparation in MALDI Imaging -- 6.3.3 MALDI Imaging of Polymers -- 6.3.4 Outlook -- 6.4 Other Surface Mass Spectrometry Methods -- 6.4.1 Desorption Electrospray Ionization -- 6.4.2 Plasma Desorption Ionization Methods -- 6.4.3 Electrospray Droplet Impact for SIMS -- 6.5 Outlook -- References -- 7 Hyphenated Techniques -- 7.1 Introduction -- 7.2 Polymer Separation Techniques -- 7.3 Principles of Coupling: Transfer Devices -- 7.3.1 Online Coupling Devices -- 7.3.2 Off-Line Coupling Devices -- 7.4 Examples -- 7.4.1 Coupling of SEC with MALDI-/ESI-MS -- 7.4.2 Coupling of LAC/LC-CC with MALDI-/ESI-MS -- 7.5 Conclusions -- References -- 8 Automated Data Processing and Quantification in Polymer Mass Spectrometry -- 8.1 Introduction -- 8.2 File and Data Formats -- 8.3 Optimization of Ionization Conditions -- 8.4 Automated Spectral Analysis and Data Reduction in MS -- 8.4.1 Long-Standing Approaches -- 8.4.2 Some New Concepts -- 8.4.3 Mass Autocorrelation -- 8.4.4 Time-Series Segmentation -- 8.5 Copolymer Analysis -- 8.6 Data Interpretation in MS/MS -- 8.7 Quantitative MS and the Determination of MMDs by MS -- 8.7.1 Quantitative MMD Measurement by MALDI-MS -- 8.7.1.1 Example for Mixtures of Monodisperse Components -- 8.7.1.2 Example for Mixtures of Polydisperse Components.

8.7.1.3 Calculating the Correction Factor for Each Oligomer -- 8.7.1.4 Step by Step Procedure for Quantitation -- 8.7.1.5 Determination of the Absolute MMD -- 8.7.2 Quantitative MMD Measurement by SEC/ESI-MS -- 8.7.2.1 Exact Measurement of the MMD of Homopolymers -- 8.7.2.2 MMD of the Individual Components in Mixtures of Functional Homopolymers -- 8.7.3 Comparison of the Two Methods for MMD Calculation -- 8.7.4 Simple Methods for the Determination of the Molar Abundance of Functional Polymers in Mixtures -- 8.8 Conclusions and Outlook -- References -- 9 Comprehensive Copolymer Characterization -- 9.1 Introduction -- 9.2 Scope -- 9.3 Reviews -- 9.4 Soft Ionization Techniques -- 9.4.1 MALDI -- 9.4.2 ESI -- 9.4.3 APCI -- 9.5 Separation Prior MS -- 9.5.1 LC-MS -- 9.5.2 Ion Mobility Spectrometry-Mass Spectrometry (IMS-MS) -- 9.6 Tandem MS (MS/MS) -- 9.7 Quantitative MS -- 9.8 Copolymers for Biological or (Bio)medical Application -- 9.9 Software Development -- 9.10 Summary and Outlook -- References -- 10 Elucidation of Reaction Mechanisms: Conventional Radical Polymerization -- 10.1 Introduction -- 10.2 Basic Principles and General Considerations -- 10.3 Initiation -- 10.3.1 Radical Generation -- 10.3.1.1 Thermally Induced Initiator Decomposition -- 10.3.1.2 Photoinduced Initiator Decomposition -- 10.3.1.3 Other Means -- 10.3.2 Initiator Efficiency -- 10.4 Propagation -- 10.4.1 Propagation Rate Coefficients -- 10.4.2 Chain-Length Dependence of Propagation -- 10.4.3 Copolymerization -- 10.5 Termination -- 10.6 Chain Transfer -- 10.6.1 Transfer to Small Molecules -- 10.6.2 Acrylate Systems -- 10.7 Emulsion Polymerization -- 10.8 Conclusion -- References -- 11 Elucidation of Reaction Mechanisms and Polymer Structure: Living/Controlled Radical Polymerization -- 11.1 Protocols Based on a Persistent Radical Effect (NMP, ATRP, and Related).

11.2 Protocols Based on Degenerative Chain Transfer (RAFT, MADIX) -- 11.3 Protocols based on CCT -- 11.4 Novel Protocols and Minor Protocols -- 11.5 Conclusions -- References -- 12 Elucidation of Reaction Mechanisms: Other Polymerization Mechanisms -- 12.1 Introduction -- 12.2 Ring-Opening Polymerization Mechanisms of Cyclic Ethers -- 12.3 Ring-Opening Polymerization Mechanisms of Cyclic Esters and Carbonates -- 12.4 Ring-Opening Metathesis Polymerization -- 12.5 Mechanisms of Step-Growth Polymerization -- 12.6 Concluding Remarks -- References -- 13 Polymer Degradation -- 13.1 Introduction -- 13.2 Thermal and Thermo-Oxidative Degradation -- 13.3 Photolysis and Photooxidation -- 13.4 Biodegradation -- 13.5 Other Degradation Processes -- 13.6 Conclusions -- References -- 14 Outlook -- Index.