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LASER DESORPTION/IONIZATION- TANDEM MASS SPECTROMETRY OF

ANTHRAQUINONE DYES AND LEAD WHITE PIGMENT FOR PAINTED WORKS OF ART

By

MICHAEL PATRICK NAPOLITANO

A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT

OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA

2013

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2013 Michael Patrick Napolitano

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To all the educators in my life who have inspired me

and nurtured my love of empiricism, science, and knowledge; and to the preservation and continuance

of the culture and heritage of the people of the Occident

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ACKNOWLEDGMENTS

Certainly, I must first humbly extend my most sincere gratitude to my research

advisor, Dr. Richard Yost. The completion of my degree would not have been possible

without his unwavering support. As my life as a chemist develops, I shall hold inviolate

his advice and hope to demonstrate that his efforts have not been in vain. I am also

very grateful for the advice from and friendship of Dr. James Horvath. During our many

discussions in his office, he instilled in me the sense of forthrightness and pride an

educator must have. I thank my committee members Dr. John Eyler, Dr. Leonid Moroz,

Dr. Nicolo Omenetto, and Dr. David Powell for their patience and guidance. Thanks are

also given to Julie Arlsanoglu, Yelena Bobkova, Dr. Phil Brucat, Dr. Mari Prieto

Conaway, Dr. Ron Heeren, Dr. Jodie Johnson, Andras Kiss, Dr. Lennaert Klerk,

Dr. Katrien Kuene, Dr. Ping-Chung Kuo, Dr. Ben Smith, and Dr. Don Smith for all of

their assistance.

I thank all the fellow students and friends that have made my time at UF

memorable and have also provided stimulating, scientific discussions including, in

alphabetical order, Dr. Dodge Baluya, Dr. Stacey Benjamin, Dr. John Bowden, Dr. Tim

Garrett, Dr. Fabrizio Guzzetta, Chris Hilton, Dr. Lloyd Horne, Dr. Kaan Kececi,

Antoinette Knight, Dr. Rachelle Landgraf, Hillary Lathrop, Jessica Leigh, Dr. Dan

Magparangalan, Dr. Antonio Masello, Dr. Rob Menger, Funda Mira, Dr. Giovennella

Moscovici, Dr. David Pirman, Karla Radke, Dr. Rich Reich, Dr. Dave Richardson, Anna

Sberegaeva, Dr. Dosung Sohn, Dr. Jennifer Garrett Williams, and Dr. Alex Wu; with

particularly special attention to Dominic Colosi, Dr. Frank Kero, Whitney Stutts, and Dr.

Marilyn Prieto Tourn. Thanks to the two NSF-REU students, Vivian Estavam-Cornlio

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and Jennifer Webber, who provided both assistance to my research and a platform to

hone my mentoring skills.

Finally, I want to thank my parents, family, and friends back home in New Jersey.

Their love and constant, unfaltering enthusiasm and support have sustained me during

my seemingly unending pursuit of higher education.

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TABLE OF CONTENTS

page

ACKNOWLEDGMENTS .................................................................................................. 4

LIST OF TABLES ............................................................................................................ 8

LIST OF FIGURES .......................................................................................................... 9

ABSTRACT ................................................................................................................... 12

CHAPTER

1 INTRODUCTION .................................................................................................... 15

Cultural Heritage ..................................................................................................... 15 Conservation Science ............................................................................................. 16

Archaeometry ................................................................................................... 16 History of Conservation Science ...................................................................... 17 Methods of Analysis ......................................................................................... 18

Instrumentation ....................................................................................................... 20 Laser Desorption/Ionization .............................................................................. 20 Matrix-Assisted Laser Desorption/Ionization .................................................... 22 Electrospray Ionization ..................................................................................... 23 Linear Quadrupole Ion Trap ............................................................................. 25 Orbitrap ............................................................................................................ 26 Figures of Merit ................................................................................................ 28

Overview of Dissertation ......................................................................................... 30

2 TANDEM MASS SPECTROMETRY OF ANTHRAQUINONES ................................. 34

Background ............................................................................................................. 34 Experimental Methods ............................................................................................ 42

Chemicals and Materials .................................................................................. 42 Recrystallization of Standards .......................................................................... 42 Preparation of Chemicals ................................................................................. 43 Electrospray Ionization Parameters .................................................................. 44 Laser Desorption/Ionization and Matrix-Assisted Laser

Desorption/Ionization Parameters ................................................................. 45 Ultravioletvisible (UV) Light Exposure ............................................................ 47

Results and Discussion........................................................................................... 47 Electrospray Ionization of Anthraquinones ....................................................... 48 Laser Desorption/Ionization of Anthraquinones ................................................ 54 Matrix-Assisted Laser Desorption/Ionization of Anthraquinones ...................... 61

Conclusion .............................................................................................................. 64

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3 TANDEM MASS SPECTROMETRY OF CLUSTERS FROM LEAD WHITE .......... 89

Background ............................................................................................................. 89 Experimental Methods .......................................................................................... 105

Chemicals and Materials ................................................................................ 105 Preparation of Chemicals ............................................................................... 105 Ionization and Instrumental Parameters ......................................................... 105

Results and Discussion......................................................................................... 107 Full-Scan Spectra Analysis ............................................................................. 107 Tandem Mass Spectrometric Analysis ........................................................... 112 Final Mass Assignments................................................................................. 115

Conclusion ............................................................................................................ 117

4 LASER DESORPTION/IONIZATION-TANDEM MASS SPECTROMETRY OF MADDER AND LEAD WHITE DIRECTLY FROM ARTISTIC SAMPLES .............. 136

Background ........................................................................................................... 136 Experimental Methods .......................................................................................... 139

Samples: Painting Fragments and Dyed Silk Swatches ................................. 139 Laser Desorption/Ionization Parameters ........................................................ 140 Instrumental Parameters ................................................................................ 141

Results and Discussion......................................................................................... 141 In Situ Detection of Alizarin from Painting Samples ....................................... 141 In Situ Detection of Madder from Swatches of Dyed Silk ............................... 142 In Situ Detection of Lead White from Painting Samples ................................. 145

Conclusion ............................................................................................................ 146

5 CONCLUSION AND FUTURE DIRECTIONS ....................................................... 161

Conclusions .......................................................................................................... 161 Future Directions .................................................................................................. 163

REFERENCES ............................................................................................................ 167

BIOGRAPHICAL SKETCH ....................................

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