1. Identification of Historical Colourants by Mass Spectrometry Volodymyr Pauk under the supervision of prof. Lemr 18.05.2012 by V.Pauk Palacky University in Olomouc Faculty of Science Department of Anlalytical Chemistry Olomouc 2012 Ref. [1]

2. Outline 1. Introduction 2. Experimental 3. Results 4. Conclusion 18.05.2012 by V.Pauk

3. Introduction 1. Identification of colourants: restoration evaluation approximate dating 2. ‘The Legend’ 18.05.2012 by V.Pauk Partial views of ‘Crucifixion’, St. Šebestian church on St. Hill in Mikulov a b c Ref. [2]

4. Introduction 3. Prussian Blue vs Indigo 18.05.2012 by V.Pauk Ref. [3, 4, 5] Prussian blueIndigo dark-blue shade small shaped particles high tinting strength highly insoluble in water and organic solvents Synthetic,18 th century, Berlin 18 th – 19 th century Natural, plant origin Antique times – 19 th century (replaced by synthetic dye) Fe 4 [Fe(CN) 6 ] 3 Iron (III) hexacyanoferrate (II ) Indigotine

5. Experimental Equipment: Micromass Q-TOF Premier, Z-spray ESI source, negative mode; Acquity UPLC system; Elma S40H ultrasound bath, 0.45 µm filters. Sample preparation: Eq. 1 Fe 4 [Fe(CN) 6 ] 3 + NaOH → Fe(OH) 3 ↓ + Na 4 [Fe(CN) 6 ] Eq. 2 Data acquisition and processing: m/z 133.95 (Prussian blue), m/z 263.08 (indigotin), Mass lynx v. 4.0 (Waters Laboratory Informatics) QC Expert v. 3.2 (TriloByte LTD.) 18.05.2012 by V.Pauk

6. a) and b) FIA mass- chronograms of Prussian blue and indigo; curves I, II, and III respond to 100, 1000 and 5000 ng/mL, respectively; integrated peak areas for 5000 ng/mL are shown; 18.05.2012 by V.PaukResults c) MS spectrum of Prussian blue d) MS spectrum of indigo Linear calibration up to 5000 ng/mL Traces of Prussian blue in samples !!! LOD: 10 ng/mL, 47 pg absolute LOD: 12 ng/mL, 59 pg absolute

7. Developed method: successful in analysis of real samples fast sensitive no chromatographic separation Application: Fast screening of Prussian blue and indigo in historical and art objects 18.05.2012 by V.PaukConclusion

8. References [1] Reproduction of Peter Paul Rubens - La découverte de la pourpre available on http://no.wikipedia.org/wiki/Fil:Peter_Paul_Rubens__La_d%C3%A9couverte_d e_la_pourpre.JPG. [2] Partial photos of the painting of ‘Crucifixion’, St. Šebestian church on St. Hill in Mikulov, Czech Republic, available on http://breclavsky.denik.cz/multimedia/galerie/2328622.html?section=1,1. [3] Kirby, J.; Saunders, D. Fading and colour change of Prussian blue: methods of manufacture and the influence of extenders. National Gallery Technical Bulletin (London), 2004, 25: 73 – 99. [4] Bartoll, J. The early use of prussian blue in paintings. 9th International Conference on NDT of Art, Jerusalem Israel, 25–30 May 2008. [5] Bechtold, T.; Mussac, R. Handbook of natural colorants. Wiley, 2009, 412 p. 18.05.2012 by V.Pauk

9. Thank You for attention 18.05.2012 by V.Pauk