UvA-DARE is a service provided by the library of the University of Amsterdam (https://dare.uva.nl)
UvA-DARE (Digital Academic Repository)
Laser desorption mass spectrometric studies of artists' organic pigments.
Wyplosz, N.
Publication date
2003
Link to publication
Citation for published version (APA):
Wyplosz, N. (2003). Laser desorption mass spectrometric studies of artists' organic pigments.
General rights
It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons).
Disclaimer/Complaints regulations
If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible.
Contents s
Chapterr 1 : Introduction 1
1.1.. Introduction 2 1.2.. Structure of an easel painting 3
1.3.. Traditional and modern organic pigments 4 1.4.. Categories of pigments under investigation 6
1.5.. Deterioration of organic pigments 8 1.6.. Investigation of organic colouring materials in conservation science 8
1.6.1.. Rationale 8 1.6.2.. Methodology 9 1.6.3.. Restriction of the analytical approach 10
1.6.4.. Molecular analysis of artists' organic pigments 11 1.7.. LDMS of organic colouring materials, a rationale 13
1.8.. Thesis outline 14 1.9.. Main results and implications for painting studies 15
Chapterr 2 : Principles and instrumentation of LDMS 17
2.1.. Introduction 18 2.2.. Laser Desorption Mass Spectrometry for Surface Analyses 19
2.3.. Principles of LDMS 21 2.3.1.. Formation of characteristic ions in LDMS 21
2.3.2.. Laser desorption and ionisation (LDI) 22 2.3.3.. Matrix-assisted laser desorption/ionisation (MALDI) 26
2.3.4.. LDI and MALDI of paint materials 28 2.4.. Instrumentation for the analysis of paint cross-section 29
2.4.1.. Mass analysers 29 2.4.2.. Time-of-flight Mass Spectrometer: Set-up and operation 30
2.4.3.. Ion Trap Mass Spectrometer: Set-up and Operation 37
2.4.4.. Multiple stage experiment with the ITMS 42
2.5.. Conclusion 44
Chapterr 3 : An experimental strategy for LDMS of paint materials 45
3.1.. Introduction 46 3.2.. Sample and sample mounting 46
3.2.1.. Sample holders 46 3.2.2.. Level differences 48 3.3.. Laser-sample interaction 50 3.4.. Shot-to-shot variations 56 3.5.. TOF-MS versus ITMS: pressure and time-scale 59
3.6.. Ion collection in the ITMS analyser: LMCO 60 3.7.. CID experiments with the ITMS analyser 62
Chapterr 4 : LDMS of flavonoids 65 5
4.1.. Introduction: 66 4.2.. Flavonoid pigments 68
4.2.1.. Materials and practice 68 4.2.2.. Molecular analysis of flavonoids and flavonoid pigments 69
4.3.. Experimental 70 4.3.1.. Instrumental set-ups 70
4.3.2.. Flavonoid samples 71 4.3.3.. Sample preparation 72 4.3.4.. Mass calibration 72 4.4.. Characterization of flavonoid aglycones with LDMS 73
4.4.11 Laser Desorption and Ionisation (LDI) 75 4.4.22 Matrix Assisted Laser Desorption Ionisation (MALDI) 79
4.5.. Multiple-stage LDI-ITMS 81 4.5.11 LDI-ITMS of kaempferol 81 4.5.22 LDI-ITMS of luteolin and fisetin 84
4.5.33 DTMS and DTMS/MS of kaempferol 86 4.5.44 LDI-ITMS of quercetin and morin, apigenin and genistein 86
4.5.55 Influence of the collisional energy in MS/MS experiments 88
4.6.. Characterisation of flavonoid-O-glycosides 89
4.6.11 LDI 89 4.6.22 MS/MS 91 4.7.. Analysis of complex samples 92
4.7.11 Weld extracts 92 4.7.22 Flavonoid lakes 93 4.8.. Analysis fibres dyed with flavonoids 94
4.9.. Investigation of cross-sectioned samples 95
4.10.. Conclusion 95
Chapterr 5 : LDMS of anthraquinones 97
5.1.. Introduction 98 5.2.. Anthraquinone pigments 98
5.2.1.. Materials and practice 98 5.2.2.. Molecular analysis of anthraquinone pigments 101
5.3.. Experimental 102 5.3.1.. Instrumental set-ups and mass calibration 102
5.3.2.. Samples 102 5.4.. LDI and MALDI of Alizarin 103
5.4.1.. Synthetic alizarin 103 5.4.2.. LDI of an alizarin lake 106 5.5.. Alizarin lake in oil paint 108 5.6.. Analysis of natural dyed fibres 108
Chapterr 6 : LDMS of indigoids 111 1
6.1.. Introduction 112 6.1.1.. Materials and practice 112
6.1.2.. Technical investigation of indigo in Conservation Sciences 114
6.1.3.. LDMS of indigo and indigo-containing samples 115
6.2.. Experimental 115 6.2.1.. Samples 115 6.2.2.. Instrumental set-ups 116
6.2.3.. Sample preparation 117 6.2.4.. Mass calibration 118 6.3.. Analysis of synthetic indigo 118
6.3.1.. LDI-TOF-MS 118 6.3.2.. MALDI-TOF-MS 122 6.3.3.. Multiple-stage LDMTMS 123 6.3.4.. LD-EI with the ITMS 126
6.3.5.. Conclusion 126 6.4.. Analysis of natural indigos 126
6.5.. LDMS of indigo at the surface of dyed fibres 128
6.6.. LDMS of indigo in oil paint 129 6.6.1.. LDMS of indigo/lead white mixtures 130
6.6.2.. Effect of laser power density 134 6.6.3.. Influence of the ratio of lead white to indigo 135
6.6.4.. LDMS of aged indigo/linseed oil mixtures 136 6.6.5.. LDMS of an indigo/linseed oil/lead white mixture 138
6.6.6.. Conclusion 139 6.7.. Spatially-resolved LDMS of cross-sections 140
6.8.. Conclusion 142
Chapterr 7 : LDMS of modern synthetic pigments 145
7.1.. Introduction 146 7.2.. Samples 149
7.2.1.. Azo pigments 150 7.2.2.. Phthalocyanines 150 7.2.3.. Quinacridones 152 7.2.4.. Perylene red pigment 153 7.2.5.. Dioxazine pigment violet PV23 154
7.2.6.. Diketopyrrolo Pyrrole Pigment Red PR 254 155 7.2.7.. Acrylic polymer emulsions (commercial tube paints) 155
7.3.. Experimental conditions 155 7.4.. Analysis of reference samples 156
7.4.1.. Napthol AS pigment red PR 188 157 7.4.2.. Diarylide pigment yellow PY83 158 7.4.3.. Cu-Phthalocyanine green PG7 159 7.4.4.. Cu-Phthalocyanine green PG36 162 7.4.5.. Quincacridones:PV19, PR206, PR207 and PR209 163
7.4.7.. Dioxazine pigment violet PV23 165 7.4.8.. Diketopyrrolo Pyrrole Pigment Red PR 254 166
7.4.9.. Conclusions 167 7.5.7.5. Acrylic polymer emulsions and oil paints 167
7.5.1.. Phthalocyanine acrylic emulsion paints 167 7.5.2.. Azo, quinacridone, dioxazine, perylene, DPP, anthraquinone 171
7.5.3.. Oil paints 175 7.5.4.. Conclusions 175 7.6.. Spatially-resolved LDMS analysis of cross-sectioned paint samples 176
7.6.1.. Reconstructed stacks of phthalocyanine layers 176 7.6.2.. Samples removed from easel paintings 177
7.7.. Conclusions 178
Chapterr 8 : Surface preparation of paint cross-sections 181
8.1.. Introduction 182 8.2.. FTIR-imaging and LD-ITMS 183
8.3.. Evidence of smearing 183 8.4.. A new sample preparation 186 8.5.. Analyses after polishing 189
8.6.. Conclusion 190 8.7.. Acknowledgements 190 Bibliographyy 191 Summaryy 198 Samenvattingg 202 Résuméé 206 Dankwoordd 210 Curriculumm Vitae 212
