Contents XXIll 14.2.8.2 Raman Spectroscopy 92 14.2.8.3 Surface Enhanced Raman Spectroscopy(SERS)93 14.2.9 Circular dichroism 14.3 NMR Spectroscopy of Proteins 94 14.3.1 Introduction 94 95 14.3.2.1 Solubility and Stability 9: 14. 3.2.2 Isotope Labeling 97 14.3.2.3 Dilute Liquid Crystals 14.3.3 Proton NMR Experiments 102 14.3.3.1 One-dimensional NMR Experiment 103 14.3.3.2 Correlation Experiments 105 14.3.3.3 Cross-relaxation Experiments 110 14.3.4 Heteronuclear NMR Experiments 113 14.3.4.1 Basic Heteronuclear Correlation Experiments 113 14.3.4. 2 Edited and Filtered Experiments 117 14.3.4.3 Triple Resonance Experiments 119 14.4 Bioanalytical Mass Spectroscopy 122 14.41 Introduction 122 14.4.2 MALDI-TOF 122 14.4.3 Electrospray Methods(ESI-MS)123 144.4 Tandem. Ms 124 14.45 TOF-SIMS 125 14.4.6 MS in Protein Analysis 126 14.4.7 MS in Nucleic Acid Analysis 130 14.5 Conclusions 130 Section VIlI Applications 2: Environmental Analysis 149 LC-MS in Environmental Analysis 152 15.1 Introduct 15.1.1 Historical Survey of the Development of LC-MS 152 15.1.2 First Applications of LC-MS 153 15.2 Applications of LC-MS Interfaces in Environmental Analyses155 15.2.1 Moving Belt Interface(MBI)156 15.2.2 Direct Liquid Introduction(DLI)156 15.2.3 Particle Beam Interface(PBI)157 15.2.4 Fast Atom Bombardment(FAB)and Continuous Flow FAB (CF-FAB)160 15.3 LC-MS Interfaces Applied in Environmental Analysis During the last decade 163 15.3.1 Achievements and obstacles 163 15.3.2 Soft Ionisation Interfaces(TSP, APCI and ESI)168
14.2.8.2 Raman Spectroscopy 92 14.2.8.3 Surface Enhanced Raman Spectroscopy (SERS) 93 14.2.9 Circular Dichroism 93 14.3 NMR Spectroscopy of Proteins 94 14.3.1 Introduction 94 14.3.2 Protein Sample 95 14.3.2.1 Solubility and Stability 95 14.3.2.2 Isotope Labeling 97 14.3.2.3 Dilute Liquid Crystals 99 14.3.3 Proton NMR Experiments 102 14.3.3.1 One-dimensional NMR Experiment 103 14.3.3.2 Correlation Experiments 105 14.3.3.3 Cross-relaxation Experiments 110 14.3.4 Heteronuclear NMR Experiments 113 14.3.4.1 Basic Heteronuclear Correlation Experiments 113 14.3.4.2 Edited and Filtered Experiments 117 14.3.4.3 Triple Resonance Experiments 119 14.4 Bioanalytical Mass Spectroscopy 122 14.4.1 Introduction 122 14.4.2 MALDI-TOF 122 14.4.3 Electrospray Methods (ESI-MS) 123 14.4.4 Tandem-MS 124 14.4.5 TOF-SIMS 125 14.4.6 MS in Protein Analysis 126 14.4.7 MS in Nucleic Acid Analysis 130 14.5 Conclusions 130 Section VIII Applications 2: Environmental Analysis 149 Introduction 151 15 LC-MS in Environmental Analysis 152 15.1 Introduction 152 15.1.1 Historical Survey of the Development of LC-MS 152 15.1.2 First Applications of LC-MS 153 15.2 Applications of LC-MS Interfaces in Environmental Analyses 155 15.2.1 Moving Belt Interface (MBI) 156 15.2.2 Direct Liquid Introduction (DLI) 156 15.2.3 Particle Beam Interface (PBI) 157 15.2.4 Fast Atom Bombardment (FAB) and Continuous Flow FAB (CF-FAB) 160 15.3 LC-MS Interfaces Applied in Environmental Analysis During the Last Decade 163 15.3.1 Achievements and Obstacles 163 15.3.2 Soft Ionisation Interfaces (TSP, APCI and ESI) 168 Contents XXIII
XXIV Contents 15.3.3 The Applications of Soft Ionising Interfaces 172 15.3.3.1 Applications Using Thermospray Ionization Interface(TSP)172 15.3.3. 2 Atmospheric Pressure Ionization Interfaces(API)183 15.4 Conclusions 226 Gas Chromatography/lon Trap Mass Spectrometry (GC/ITMS) for Environmental Analysis 244 16.1 Introduction 244 16.2 Practical Aspects of GC/ITMs 245 Historical survey 245 16.2.2 Principles of Operation 245 16.2.3 Ionization and scanning modes 247 16.2.3.1 Electron Ionization 247 16.2.3.2 Chemical ionization 249 16.2.3,3 Full Scan versus selected-Ion monitoring 251 16.2.4 Advances in GC/ITMs 251 16.2.4.1 Methods for Improving Performances Increasing the Signal-to-Background Ratio 252 16.2.4.2 External Ion Sources 252 1624.3GC/MS/Ms253 16.3 Examples of Applications of GC/ITMS 254 16.3.1 Requirements for Environmental Analysis 254 16. 3. 2 Determination of Volatile Organic Compounds in Drinking Water EPA Methods 256 16.3.3 Detection of dioxins and furans 257 16.3.4 Other Examples 258 16.4 Future Prospects in GC/Chemical lonization-ITMS 260 16.4.1 Chemical Ionization in Environmental Analysis 260 16.4.2 Examples of Unusual Reagents for Chemical Ionization 26 16.4.3 Ion Attachment Mass Spectrometry 262 16.4.3.1 Principle 262 16. 4.3.2 Sodium Ion Attachment Reactions with GC/ITMS 263 16.6 Appendix: List of Main Manufacturers and Representative Products for GC/ITMS 266 Section IX Application 3: Process Control 268 Introduction 269 Optical Spectroscopy 17.1 172 Mid-infrared 173 Non-dispersive Infrared Analysers 28 174 Near-infrared Spectroscopy 282
15.3.3 The Applications of Soft Ionising Interfaces 172 15.3.3.1 Applications Using Thermospray Ionization Interface (TSP) 172 15.3.3.2 Atmospheric Pressure Ionization Interfaces (API) 183 15.4 Conclusions 226 16 Gas Chromatography/Ion Trap Mass Spectrometry (GC/ITMS) for Environmental Analysis 244 16.1 Introduction 244 16.2 Practical Aspects of GC/ITMS 245 16.2.1 Historical survey 245 16.2.2 Principles of Operation 245 16.2.3 Ionization and Scanning Modes 247 16.2.3.1 Electron Ionization 247 16.2.3.2 Chemical ionization 249 16.2.3.3 Full Scan Versus Selected-Ion Monitoring 251 16.2.4 Advances in GC/ITMS 251 16.2.4.1 Methods for Improving Performances: Increasing the Signal-to-Background Ratio 252 16.2.4.2 External Ion Sources 252 16.2.4.3 GC/MS/MS 253 16.3 Examples of Applications of GC/ITMS 254 16.3.1 Requirements for Environmental Analysis 254 16.3.2 Determination of Volatile Organic Compounds in Drinking Water; EPA Methods 256 16.3.3 Detection of Dioxins and Furans 257 16.3.4 Other Examples 258 16.4 Future Prospects in GC/Chemical Ionization-ITMS 260 16.4.1 Chemical Ionization in Environmental Analysis 260 16.4.2 Examples of Unusual Reagents for Chemical Ionization 261 16.4.3 Ion Attachment Mass Spectrometry 262 16.4.3.1 Principle 262 16.4.3.2 Sodium Ion Attachment Reactions with GC/ITMS 263 16.5 Conclusion 265 16.6 Appendix: List of Main Manufacturers and Representative Products for GC/ITMS 266 Section IX Application 3: Process Control 268 Introduction 269 17 Optical Spectroscopy 279 17.1 Introduction 279 17.2 Mid-infrared 281 17.3 Non-dispersive Infrared Analysers 281 17.4 Near-infrared Spectroscopy 282 XXIV Contents
Raman Spectroscopy 287 Laser Diode Techniques 291 Chemiluminescence 293 17.11 18 NMR 297 18.1 Introductio 18.2 Motivations for Using NMR in Process Control 297 18.3 Broadline nmr 184 FT-NMR 307 18.5 Conclusion 314 Process Mass Spectrometry 316 19.2 Hardware Technology 317 19.2.1 319 19.2.2 Sample Inlet 319 19.2.2.1 Direct Capillary Inlets 320 19.2.2.2 Membrane inlets 320 19.2.2.3 Gas Chromatography(GC) 320 19.2.3 lonization 321 19.2.4 Mass Analyzers 32 19.2.4.1 Sector Mass Analyzers 322 19.2.4. 2 Quadrupole Mass Analyzers 323 19.2.4.3 Choice of Analyzer 324 19.25 Detectors 3 19. 2.6 Vacuum System 325 19.2.7 Data Analysis and Output 325 19.2.8 Calibration System 327 19.2.9 Gas Cylinders 328 19.2.10 Permeation Devices 328 19.2.11 Sample Loops 329 19.2. Requirements 3 19.2. 13 Modes of Operation 329 19.3 Applications 330 19.3.1 Example Application: Fermentation Off-gas Analysis 331 19.4 Summary 334 20 Elemental Analysis 336 20.1 Applications of Atomic Spectrometry in Process Analysis 336 20.1.1 Catalyst Control 337 20.1.2 Corrosion Monitoring 339
17.5 Ultraviolet/Visible Spectroscopy 286 17.6 Raman Spectroscopy 287 17.7 Laser Diode Techniques 291 17.8 Fluorescence 293 17.9 Chemiluminescence 293 17.10 Optical Sensors 294 17.11 Cavity Ringdown Spectroscopy 294 18 NMR 297 18.1 Introduction 297 18.2 Motivations for Using NMR in Process Control 297 18.3 Broadline NMR 301 18.4 FT-NMR 307 18.5 Conclusion 314 19 Process Mass Spectrometry 316 19.1 Introduction 316 19.2 Hardware Technology 317 19.2.1 Sample Collection and Conditioning 319 19.2.2 Sample Inlet 319 19.2.2.1 Direct Capillary Inlets 320 19.2.2.2 Membrane Inlets 320 19.2.2.3 Gas Chromatography (GC) 320 19.2.3 Ionization 321 19.2.4 Mass Analyzers 322 19.2.4.1 Sector Mass Analyzers 322 19.2.4.2 Quadrupole Mass Analyzers 323 19.2.4.3 Choice of Analyzer 324 19.2.5 Detectors 325 19.2.6 Vacuum System 325 19.2.7 Data Analysis and Output 325 19.2.8 Calibration System 327 19.2.9 Gas Cylinders 328 19.2.10 Permeation Devices 328 19.2.11 Sample Loops 329 19.2.12 Maintenance Requirements 329 19.2.13 Modes of Operation 329 19.3 Applications 330 19.3.1 Example Application: Fermentation Off-gas Analysis 331 19.4 Summary 334 20 Elemental Analysis 336 20.1 Applications of Atomic Spectrometry in Process Analysis 336 20.1.1 Catalyst Control 337 20.1.2 Corrosion Monitoring 339 Contents XXV
XXVI Contents 20.1.3 Reducing Environmental Impact 341 20.1.4 Troubleshooting Process Problems 342 On-stream/at-line Analysis 343 20.2.1 X-ray Fluorescence(XRF) 344 20.2.1.1 Liquid Process Streams 348 0. 2. 1.2 Trace Analysis and Corrosion Monitoring 351 0. 2.1.3 Analysis of Slurries and Powders 352 20.2.1.4 Direct Analysis 354 20.2.2 Atomic Emission Spectrometry 356 20.2.2.1 Plasma Spectrometry 356 0. 2.2.2 Laser Based Techniques 362 Section X Hyphenated Techniques 377 Introduction 379 21 Hyphenated Techniques for Chromatographic Detection 381 21.1 Introduction 381 21.2 Electronic Spectral Detection 383 214 NMR Detection 412 21.5 FTIR Detection 415 21.6 Atomic Spectrometric Detection 421 21.7 Other Types of Detection 428 Serial or Parallel Multiple Detection 430 Section XI General Data Treatment: Data Bases/Spectral Libaries 437 Optical Spectroscopy 441 Introduction 44 22.2 tons 442 22.2.1 Centering 442 22.2.2 Standardization(Autoscaling)443 22.3 Evaluation of Spectra 444 22.3.1 Introduction 444 22.3.2 Qualitative Evaluation of Spectra 446 22 3.2.1 Spectral Data Banks 446 22 3.2.2 Data Banks Containing Spectroscopic Information 452 22 3.2.3 Interpretation of Spectra by Means of Group Frequencies and of Characteristic Bands 452 22 3.2.4 PCA(Principal Component Analysis)452 22.3.2.5 Cluster Analysis 455
20.1.3 Reducing Environmental Impact 341 20.1.4 Troubleshooting Process Problems 342 20.2 On-stream/at-line Analysis 343 20.2.1 X-ray Fluorescence (XRF) 344 20.2.1.1 Liquid Process Streams 348 20.2.1.2 Trace Analysis and Corrosion Monitoring 351 20.2.1.3 Analysis of Slurries and Powders 352 20.2.1.4 Direct Analysis 354 20.2.2 Atomic Emission Spectrometry 356 20.2.2.1 Plasma Spectrometry 356 20.2.2.2 Laser Based Techniques 362 20.3 Conclusions 368 Section X Hyphenated Techniques 377 Introduction 379 21 Hyphenated Techniques for Chromatographic Detection 381 21.1 Introduction 381 21.2 Electronic Spectral Detection 383 21.3 MS Detection 400 21.4 NMR Detection 412 21.5 FTIR Detection 415 21.6 Atomic Spectrometric Detection 421 21.7 Other Types of Detection 428 21.8 Serial or Parallel Multiple Detection 430 Section XI General Data Treatment: Data Bases/Spectral Libaries 437 Introduction 439 22 Optical Spectroscopy 441 22.1 Introduction 441 22.2 Basic Operations 442 22.2.1 Centering 442 22.2.2 Standardization (Autoscaling) 443 22.3 Evaluation of Spectra 444 22.3.1 Introduction 444 22.3.2 Qualitative Evaluation of Spectra 446 22.3.2.1 Spectral Data Banks 446 22.3.2.2 Data Banks Containing Spectroscopic Information 452 22.3.2.3 Interpretation of Spectra by Means of Group Frequencies and of Characteristic Bands 452 22.3.2.4 PCA (Principal Component Analysis) 452 22.3.2.5 Cluster Analysis 455 XXVI Contents
22.3.2.6 Discriminant analysis 4 22.3.2.7 SIMCA Soft Independent Modeling of Class Analogy(SIMCA)453 22.3.3 Quantitative Evaluation of Spectra 455 223.31 Univariate Methods 456 2.3.3.2 Multivariate methods 459 Nuclear Magnetic Resonance Spectroscopy 469 Introduct 23.2 Comparison of NMR-Spectroscopy with IR and Ms 470 23.3 Methods in NMR Spectroscopy 471 23.4 Spectral Similarity Search Techniques 471 23.5 Spectrum Estimation, Techniques 473 23.6 Spectrum Prediction, Quality Consideration 474 23.7 Spectrum Prediction and Quality Control, Examples475 Spectrum Interpretation and Isomer Generation 481 23.9 Ranking of Candidate Structures 484 23.10 Conclusions 484 24.1 Introduction488 24.2 Mass Spectrometry Databases 489 24.2.1 NIST/EPA/NIH Mass Spectral Library 490 24. 2.2 Wiley Registry of Mass Spectral Data 491 24.2.4 SDBS, Integrated Spectra Data Base System for Organic Compounds 492 24.2.5 Other Smaller Collections 492 24 2.5.1 Pfleger/Maurer/ Weber: Mass Spectral and GC Data of Drugs, Poisons, Pesticides, pollutants and their metabolites 494 24.2.5.2 Ehrenstorfer 494 24.2.5.3 Wiley-SIMS 494 24.2.5.4 American Academy of Forensic Sciences, Toxicology Section, Mass Spectrometry Database Committee 494 24.2.5.5 The International Association of Forensic Toxicologists(TIAFt)494 24.3 Mass Spectrometry Search Software 495 24.3.1 INCOS496 24.3.2 Probability Based Matching(PBM)496 24.3.3 MassLib/ SISCOM 497 24.3.4 AMDIS498 243.5 Mass Frontier 499 243.6 The Web Book 500 24.3. 7 General Spectroscopy Packages 501 24.4 Biological Mass Spectrometry and General Works 502 Index 505
22.3.2.6 Discriminant analysis 455 22.3.2.7 SIMCA Soft Independent Modeling of Class Analogy (SIMCA) 455 22.3.3 Quantitative Evaluation of Spectra 455 22.3.3.1 Univariate Methods 456 22.3.3.2 Multivariate Methods 459 23 Nuclear Magnetic Resonance Spectroscopy 469 23.1 Introduction 469 23.2 Comparison of NMR-Spectroscopy with IR and MS 470 23.3 Methods in NMR Spectroscopy 471 23.4 Spectral Similarity Search Techniques 471 23.5 Spectrum Estimation, Techniques 473 23.6 Spectrum Prediction, Quality Consideration 474 23.7 Spectrum Prediction and Quality Control, Examples 475 23.8 Spectrum Interpretation and Isomer Generation 481 23.9 Ranking of Candidate Structures 484 23.10 Conclusions 484 24 Mass spectrometry 488 24.1 Introduction 488 24.2 Mass Spectrometry Databases 489 24.2.1 NIST/EPA/NIH Mass Spectral Library 490 24.2.2 Wiley Registry of Mass Spectral Data 491 24.2.3 SpecInfo/SpecData 491 24.2.4 SDBS, Integrated Spectra Data Base System for Organic Compounds 492 24.2.5 Other Smaller Collections 492 24.2.5.1 Pfleger/Maurer/Weber: Mass Spectral and GC Data of Drugs, Poisons, Pesticides, Pollutants and Their Metabolites 494 24.2.5.2 Ehrenstorfer 494 24.2.5.3 Wiley-SIMS 494 24.2.5.4 American Academy of Forensic Sciences, Toxicology Section, Mass Spectrometry Database Committee 494 24.2.5.5 The International Association of Forensic Toxicologists (TIAFT) 494 24.3 Mass Spectrometry Search Software 495 24.3.1 INCOS 496 24.3.2 Probability Based Matching (PBM) 496 24.3.3 MassLib/SISCOM 497 24.3.4 AMDIS 498 24.3.5 Mass Frontier 499 24.3.6 The WebBook 500 24.3.7 General Spectroscopy Packages 501 24.4 Biological Mass Spectrometry and General Works 502 Index 505 Contents XXVII