Introduction Derivatisation principles for electron and chemical ionisation mass spectrometry and gas chromatography/mass spectrometry Derivatisation principles in soft-ionisation mass spectrometry References 1. Silylation 1.1 Introduction 1.2. Chemical aspects of silylation 1.3. Chromatographic properties of silyl derivatives 1.4. Mass spectral properties of silyl derivatives 1.5. Analytical applications 1.6. References 2. Acylation 2.1 Introduction 2.2 Chemical aspects of acylation 2.3 Some mass spectral properties of acyl derivatives 2.4 Some analytical applications 2.5 References 3. Alkylation (arylation) 3.1 Introduction 3.2 Chemical aspects of alkylation (arylation) reactions 3.3 Some mass spectral features of alkyl (aryl) derivatives 3.4 Some common analytical applications of alkylation 3.5 References 4. Formation of cyclic derivatives 4.1 Introduction 4.2 Cyclic acetals and ketals 4.3 Cyclic boronates 4.4 Cyclic siliconides (or dialkylsilylene derivatives) 4.5 Cyclic carbonates 4.6 Cyclic derivatives of amino acids 4.7 Miscellaneous cyclic derivatives 4.8 References 5. Specific derivatisation of monofunctional compounds 5.1 Introduction 5.2 Derivatisation of unsaturated compounds 5.3 Derivatisation of oxirane- or cyclopropane-containing compounds 5.4 Derivatisation of alcohols 5.5 Derivatisation of amines 5.6 Derivatisation of carboxylic acids 5.7 Derivatisation of aldehydes and ketones 5.8 Miscellaneous derivatisations 5.9 Derivatisation for the differentiation and determination of chiral enantiomers 5.10 Degradation of compounds before mass investigation 5.11 References 6. Formation of mixed derivatives of polyfunctional compounds 6.1 Introduction 6.2 Mixed derivatives of amino acids and oligopeptides 6.3 Mixed derivatives of amino alcohols and amino ketones 6.4 Mixed derivatives of hydroxy acids 6.5 Mixed derivatives of oxo acids 6.6 Mixed derivatives of oxo alcohols 6.7 Mixed derivatives of polyols and compounds containing both phenolic and alcoholic hydroxyls 6.8 Mixed derivatives of compounds containing simultaneously hydroxy, oxo and carboxyl groups 6.9 Miscellaneous mixed derivatisation 6.10 References 7. On-line derivatisation/degradation 7.1 Introduction 7.2 On-line chemical reactions in a microreactor connected directly to a mass spectrometer 7.3 On-line chemical reactions in the flash-heater of a GC/MS system 7.4 On-line chemical reactions in a microreactor located before the gas chromatographic column (pre-column derivatisation) 7.4.1 Catalytic microreactions 7.5 On-column derivatisation in GC/MS 7.6 Derivatisation/degradation in a microreactor situated between a chromatographic column and a mass spectrometer (post-column derivatisation) 7.7 Post-column derivatisation in HPLC/MS 7.8 References 8. Soft ionisation mass spectrometry of small molecules 8.1 Introduction 8.2 Derivatisation of amines 8.3 Derivatisation of carboxyl groups 8.4 Derivatisation of amino acids 8.5 Derivatisation of hydroxyl groups including A--phenolics 8.6 Derivatisation of carbonyl groups 8.7 Derivatisation of small carbohydrates 8.8 Derivatisation of mercapto groups 8.9 Derivatisation of unsaturated and aromatic compounds 8.10 Derivatisation of miscellaneous compounds 8.11 Derivatisation of multifunctional compounds by silylation 8.12 Derivatisation in other softA" ionisation mass spectrometric methods 8.13 References 9. Soft ionisation mass spectrometry of large molecules 9.1 Introduction 9.2 Derivatisation of proteins and oligopeptides 9.3 Derivatisation of oligosaccharides 9.4 Derivatisation of synthetic polymers 9.5 Conclusions 9.6 References Appendix Table A.1. Common functional groups and some major derivatisations. Table A.2. Popular derivatisations for the GC/MS analysis of selected compound classes in biological A--matrices. Table A.3. Some derivatisation methods for particular functional groups for softA"-ionisation mass A--spectrometry. Table A.4. Some N-terminal charge derivatisations and sequence-related ions. Table A.5. Some chemical stable isotope coding strategies of various reactive centres for sequence and A--quantitative determinations of proteins and peptides. Index.