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Mass Spectrometry Methods for the Analysis Of MASS SPECTROMETRY METHODS FOR THE ANALYSIS OF POLYMERS AND BIOCONJUGATES A Dissertation Presented to The Graduate Faculty of the University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Sahar Sallam December, 2017 MASS SPECTROMETRY METHODS FOR THE ANALYSIS OF POLYMERS AND BIOCONJUGATES Sahar Sallam Dissertation Approved: Accepted: __________________________________ __________________________________ Advisor Department Chair Dr. Chrys Wesdemiotis Dr. Christopher J. Ziegler ____________________________________________________________________ Committee Member Dean of the Collage Dr. Wiley J. Youngs Dr. John C. Green ___________________________________________________________________ Committee Member Dean of the Graduate School Dr. Yi Pang Dr. Chand K. Midha ____________________________________________________________________ Committee Member Date Dr. Sailaja Paruchuri __________________________________ Committee Member Dr. Matthew L. Becker ii ABSTRACT This dissertation focuses on the characterization of complex biomaterials by mass spectrometry (MS), tandem mass spectrometry (MS/MS) and ion mobility mass spectrometry (IM-MS). Chapter I provides a brief summary of the analytical problems addressed in this dissertation. Chapter II discusses the basic principles of mass spectrometry, including ionization techniques, mass analyzers, tandem mass spectrometry, and ion mobility. Chapter III describes the materials and instruments used to accomplish this work. Chapters IV, V, VI and VII are research project chapters, and each is briefly introduced below. Finally, Chapter VIII summarizes the conclusions drawn from this dissertation followed by an appendix and the copyright permissions obtained for this dissertation. The analysis of isomeric biodegradable polyesters is discussed in chapter IV. Matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) coupled with time-of-flight (ToF) mass analysis and tandem mass spectrometry (MS2) fragmentation were used to elucidate the composition, end groups, the chain sequence of poly(propylene maleate) (PPM) and poly(propylene fumarate) (PPF) copolymers. Additionally, ion mobility mass spectrometry (IM-MS) was used to differentiate the isomeric PPM and PPF copolyesters and to probe the extent and efficiency of PPM to PPF (i.e., all-cis to all-trans) isomerization. The analysis of the alanine-rich peptides AQK18 and GpAQK18 and their poly(ethylene glycol)-conjugated (PEGylated) forms AQK18-PEG and GpAQK18-PEG, iii is discussed in chapter V. In this work, ESI and MALDI interfaced with MS2 fragmentation and shape-sensitive separation via ion mobility mass spectrometry (IM- MS), were applied to elucidate the sequence and conformation of alanine-rich polypeptides and their conjugates. IM-MS data revealed the existence of two conformers for both the polypeptides and the conjugates. These were assigned to a fast-drifting random coil and a more slowly drifting helical structure. The collision cross- sections of the random coil and helical conformers of the polypeptides and their PEG conjugates were simulated for comparison with the experimental values to confirm the identity of the observed architectures and understand the stabilizing effects of the polymer chain. Chapter VI focuses on the structural characterization of a branched glycopolymer. Reversible addition-fragmentation chain transfer (RAFT) copolymerization of galactose acrylate and a polymerizable chain transfer agent branching unit was used to prepare this glycopolymer. Multistage mass spectrometry (MSn) and ion mobility were employed in this work to unveil useful information about the glycopolymer composition, possible end groups and architecture. Chapter VII discusses the analysis of a trehalose glycopolymer and its insulin conjugate. The goal of this study was to provide full characterization and detailed information about the chemical composition of the trehalose glycopolymer and its insulin conjugate and to determine the degree and the sites of conjugation by using multidimensional MS, including MALDI-MS, ESI-MS, and MS2. iv DEDICATION To my husband Ehab Zakri and my wonderful daughters (Lojain, Faridah and Emadiah) who encouraged and supported me and made this possible. To my lovely parents Awad Sallam and Faridah Abu Gazala for their love and unlimited support. v ACKNOWLEDGEMENTS First of all, I would like to thank Almighty Allah (God) for giving me the opportunity, strength, and knowledge to commence this research study. Without His blessings, this achievement would be impossible. I would also like to express my sincere gratitude to my advisor Dr. Chrys Wesdemiotis for his guidance, kindness, and assistance during my study at the University of Akron. It was a pleasure to work under his supervision during my research work as he was always available and willing to help. Thanks are also due to my committee members Dr. Sailaja Paruchuri, Dr. Yi Pang, Dr. Willy Youngs and Dr. Matthew L. Becker for serving as my committee members, spending their valuable time to correct my dissertation, and giving me invaluable guidance and suggestions. I would like to thank and acknowledge the Ministry of Higher Education and Jazan University, Kingdom of Saudi Arabia for giving me the opportunity to pursue my graduate studies and supporting me through the past four years. Also, I would like to express my gratitude to the Department of Chemistry at the University of Akron for their extensive comments and assistance during my study. In particular, I would like to thank my collaborators at Dr. Becker’s group (from the University of Akron), Dr. Jia’s group (from the University of Delaware), Dr. vi Maynard’s group and Dr. Kasko’s group (from the University of California Los Angeles) for their support and for providing me the samples used in this dissertation. Special thanks go to the past group members Dr. Nadrah Alawani, Dr. Ahlam Alalwiat, Dr. Xiumin Liu, Dr. Kai Guo and Dr. Lydia Cool for sharing their knowledge and expertise in mass spectrometry with me. Further thanks go to the current group members Dr. Ivan Dolog, Nicolas Alexander, Selim Gerislioglu, Kevin Endres, Michelle Kushnir, Jialin Mao, Savannah Snyder, Jason O’Neill and Chen Du for their friendship, help and support. I also wish to thank all my Akron friends for their friendship and support over the past years. They have always made me feel welcomed and never left my side. My acknowledgement would be incomplete without thanking the main source of my strength, my family. The unlimited love and support of my parents (Mr. Awad Sallam & Mrs. Faridah Abu Gazala), my sisters (Samar, Sumyyah and Samah) and my brothers (Sallam, Mohamed and Ali) have made this project possible. Finally, no words can express how grateful and thankful I am to have my lovely husband Ehab Zakri and my adorable daughters (Lojain, Faridah, and Emadiah) in my life. You’ve always believed in me and stood by my side during hard times. vii TABLE OF CONTENTS LIST OF TABLES ......................................................................................................................... xii LIST OF FIGURES ...................................................................................................................... xiii LIST OF SCHEMES .................................................................................................................... xx ACRONYMNS AND ABBREVIATIONS ....................................................................................... xxi CHAPTER I. INTRODUCTION ................................................................................................................. 1 II. MASS SPECTROMETRY BACKGROUND ........................................................................ 6 2.1. Mass Spectrometry ................................................................................................... 6 2.1.1. Ionization methods ..................................................................................... 7 2.1.2. Mass Analyzers........................................................................................ 14 2.1.3 Detectors .................................................................................................. 23 2.2. Tandem Mass Spectrometry ................................................................................... 25 2.2.1 Collisionally Activated Dissociation.......................................................... 28 2.2.2 Electron Transfer Dissociation (ETD) ...................................................... 28 2.3 Ion mobility (IM-MS) ................................................................................................ 28 III. MATERIALS AND INSTRUMENTATION ......................................................................... 34 3.1 Materials ................................................................................................................. 34 3.2 Instrumentation ...................................................................................................... 35 3.2.1 Ultraflex III ToF/ToF Mass Spectrometer ............................................... 35 3.2.2 Synapt HDMS Mass Spectrometer .......................................................... 36 viii 3.2.3 HCT Ultra II ESI-QIT Mass Spectrometer .............................................. 38 IV. MULTIDIMENSIONAL MASS SPECTROMETRY CHARACTERIZATION OF ISOMERIC BIODEGRADABLE POLYESTERS .................................................................................. 40 4.1 Introduction............................................................................................................
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