Introduction 1 Christopher Barner-Kowollik, Jana Falkenhagen, Till Gruendling, and Steffen Weidner References 4

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1 V Contents List of Contributors XIII Introduction 1 Christopher Barner-Kowollik, Jana Falkenhagen, Till Gruendling, and Steffen Weidner References 4 1 Mass Analysis 5 Gene Hart-Smith and Stephen J. Blanksby 1.1 Introduction Measures of Performance Mass Resolving Power Mass Accuracy Mass Range Linear Dynamic Range Abundance Sensitivity Instrumentation Sector Mass Analyzers Quadrupole Mass Filters D Ion Traps Linear Ion Traps Time-of-Flight Mass Analyzers Fourier Transform Ion Cyclotron Resonance Mass Analyzers Orbitraps Instrumentation in Tandem and Multiple-Stage Mass Spectrometry Conclusions and Outlook 29 References 30 2 Ionization Techniques for Polymer Mass Spectrometry 33 Anthony P. Gies 2.1 Introduction Small Molecule Ionization Era 34

2 VI Contents Electron Ionization (EI) Chemical Ionization (CI) Pyrolysis Mass Spectrometry (Py-MS) Macromass Era of Ionization Field Desorption (FD) and Field Ionization (FI) Secondary Ion Mass Spectrometry (SIMS) Fast Atom Bombardment (FAB) and Liquid Secondary Ion Mass Spectrometry (LSIMS) Laser Desorption (LD) Plasma Desorption (PD) Other Ionization Methods Modern Era of Ionization Techniques Electrospray Ionization (ESI) New Trends Atmospheric Pressure Chemical Ionization (APCI) New Trends Matrix-Assisted Laser Desorption/Ionization (MALDI) New Trends Conclusions 53 References 53 3 Tandem Mass Spectrometry Analysis of Polymer Structures and Architectures 57 Vincenzo Scionti and Chrys Wesdemiotis 3.1 Introduction Activation Methods Collisionally Activated Dissociation (CAD) Surface-Induced Dissociation (SID) Photodissociation Methods Electron Capture Dissociation and Electron Transfer Dissociation (ECD/ETD) Post-Source Decay (PSD) Instrumentation Quadrupole Ion Trap (QIT) Mass Spectrometers Quadrupole/time-of-flight (Q/ToF) Mass Spectrometers ToF/ToF Instruments Structural Information from MS 2 Studies End-Group Analysis and Isomer/Isobar Differentiation Polymer Architectures Copolymer Sequences Assessment of Intrinsic Stabilities and Binding Energies Summary and Outlook 78 References 79

3 Contents VII 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 85 Christopher B. Lietz, Alicia L. Richards, Darrell D. Marshall, Yue Ren, and Sarah Trimpin 4.1 Overview Introduction New Sample Introduction Technologies Laserspray Ionization Ion Mobility Spectrometry-Mass Spectrometry Matrix Assisted Inlet Ionization (MAII) LSIV in Reflection Geometry at Intermediate Pressure (IP) Fragmentation by ETD and CID Surface Analyses by Imaging MS Ultraf Fast LSII-MS Imaging in Transmission Geometry (TG) LSIV-IMS-MS Imaging in Reflection Geometry (RG) Future Outlook 109 References Polymer MALDI Sample Preparation 119 Scott D. Hanton and Kevin G. Owens 5.1 Introduction Roles of the Matrix Intimate Contact Absorption of Laser Light Efficient Desorption Effective Ionization Choice of Matrix Choice of the Solvent Basic Solvent-Based Sample Preparation Recipe Deposition Methods Solvent-Free Sample Preparation The Vortex Method Matrix-to-Analyte Ratio Salt-to-Analyte Ratio Chromatography as Sample Preparation Problems in MALDI Sample Preparation Predicting MALDI Sample Preparation Conclusions 143 References Surface Analysis and Imaging Techniques 149 Christine M. Mahoney and Steffen M. Weidner 6.1 Imaging Mass Spectrometry Secondary Ion Mass Spectrometry 150

4 VIII Contents Static SIMS of Polymers The Fingerprint Region High-Mass Region Imaging in Polymer Blends and Multicomponent Systems Data Analysis Methods Polymer Depth Profiling with Cluster Ion Beams A Brief Discussion on the Physics and Chemistry of Sputtering and its Role in Optimized Beam Conditions D Analysis in Polymer Systems Matrix-Assisted Laser Desorption Ionization (MALDI) History of MALDI Imaging Mass Spectrometry Sample Preparation in MALDI Imaging MALDI Imaging of Polymers Outlook Other Surface Mass Spectrometry Methods Desorption Electrospray Ionization Plasma Desorption Ionization Methods Electrospray Droplet Impact for SIMS Outlook 196 References Hyphenated Techniques 209 Jana Falkenhagen and Steffen Weidner 7.1 Introduction Polymer Separation Techniques Principles of Coupling: Transfer Devices Online Coupling Devices Off-Line Coupling Devices Examples Coupling of SEC with MALDI-/ESI-MS Coupling of LAC/LC-CC with MALDI-/ESI-MS Conclusions 228 References Automated Data Processing and Quantification in Polymer Mass Spectrometry 237 Till Gruendling, William E. Wallace, Christopher Barner-Kowollik, Charles M. Guttman, and Anthony J. Kearsly 8.1 Introduction File and Data Formats Optimization of Ionization Conditions Automated Spectral Analysis and Data Reduction in MS Long-Standing Approaches Some New Concepts Mass Autocorrelation 243

5 Contents IX Time-Series Segmentation Copolymer Analysis Data Interpretation in MS/MS Quantitative MS and the Determination of MMDs by MS Quantitative MMD Measurement by MALDI-MS Example for Mixtures of Monodisperse Components Example for Mixtures of Polydisperse Components Calculating the Correction Factor for Each Oligomer Step by Step Procedure for Quantitation Determination of the Absolute MMD Quantitative MMD Measurement by SEC/ESI-MS Exact Measurement of the MMD of Homopolymers MMD of the Individual Components in Mixtures of Functional Homopolymers Comparison of the Two Methods for MMD Calculation Simple Methods for the Determination of the Molar Abundance of Functional Polymers in Mixtures Conclusions and Outlook 276 References Comprehensive Copolymer Characterization 281 Anna C. Crecelius and Ulrich S. Schubert 9.1 Introduction Scope Reviews Soft Ionization Techniques MALDI ESI APCI Separation Prior MS LC-MS Ion Mobility Spectrometry-Mass Spectrometry (IMS-MS) Tandem MS (MS/MS) Quantitative MS Copolymers for Biological or (Bio)medical Application Software Development Summary and Outlook 309 References Elucidation of Reaction Mechanisms: Conventional Radical Polymerization 319 Michael Buback, Gregory T. Russell, and Philipp Vana 10.1 Introduction Basic Principles and General Considerations Initiation 321

6 X Contents Radical Generation Thermally Induced Initiator Decomposition Photoinduced Initiator Decomposition Other Means Initiator Efficiency Propagation Propagation Rate Coefficients Chain-Length Dependence of Propagation Copolymerization Termination Chain Transfer Transfer to Small Molecules Acrylate Systems Emulsion Polymerization Conclusion 365 References Elucidation of Reaction Mechanisms and Polymer Structure: Living/Controlled Radical Polymerization 373 Christopher Barner-Kowollik, Guillaume Delaittre, Till Gruendling, and Thomas Paulöhrl 11.1 Protocols Based on a Persistent Radical Effect (NMP, ATRP, and Related) Protocols Based on Degenerative Chain Transfer (RAFT, MADIX) Protocols based on CCT Novel Protocols and Minor Protocols Conclusions 398 References Elucidation of Reaction Mechanisms: Other Polymerization Mechanisms 405 Gra_zyna Adamus and Marek Kowalczuk 12.1 Introduction Ring-Opening Polymerization Mechanisms of Cyclic Ethers Ring-Opening Polymerization Mechanisms of Cyclic Esters and Carbonates Ring-Opening Metathesis Polymerization Mechanisms of Step-Growth Polymerization Concluding Remarks 430 References Polymer Degradation 437 Paola Rizzarelli, Sabrina Carroccio, and Concetto Puglisi 13.1 Introduction Thermal and Thermo-Oxidative Degradation 438

7 Contents XI 13.3 Photolysis and Photooxidation Biodegradation Other Degradation Processes Conclusions 457 References Outlook 467 Christopher Barner-Kowollik, Jana Falkenhagen, Till Gruendling, and Steffen Weidner Index 469

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