Broadband Phase Correction of Fourier Transform Ion Cyclotron Mass Spectra
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Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2012 Broadband Phase Correction of Fourier Transform Ion Cyclotron Resanonce Mass Spectra Feng Xian Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] THE FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES BROADBAND PHASE CORRECTION OF FOURIER TRANSFORM ION CYCLOTRON RESANONCE MASS SPECTRA By FENG XIAN A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy Degree Awarded: Spring Semester, 2012 Feng Xian defended this dissertation on March 30, 2012. The members of the supervisory committee were: Alan G. Marshall Professor Directing Dissertation Christopher L. Hendrickson Professor Co-Directing Dissertation Stephen Hill University Representative Naresh S. Dalal Committee Member Michael Roper Committee Member The Grduate School has verified and approved the above-named committee members, and certifies that the dissertation has been approved in accordance with university requirements. ii To my parents, Huaiyun Xian and Mingxiang Gao; my wife, Donghong Min; my daughter, Stephanie Xian, my son, Anthony Xian. iii ACKNOWLEDGEMENTS I am sincerely and heartily grateful to my supervisor, Dr. Alan G. Marshall, for his excellent guidance, caring and support. Dr. Marshall gives me valuable suggestions on how to become a successful scientist and provides me with a scientific environment for doing research. I am sure that it would have not been possible without his patient and intelligent advising. I would also like to thank Dr. Stephen Hill, Dr. Naresh S. Dalal and Dr. Michael Roper for their inspiring suggestions, their time and effort to serve on my examination committee. I would also like to thank Dr. Chris Hendrickson for teaching me basically everything that I know about mass spectrometry. His valuable suggestions and helpful discussions are very important part in my research. I also thank Dr. Steve Beu for his expertise in the fields of FT- ICR instrumentation and Dr. Greg Blakney for technical support in software development. I would like to thank all the former and current members in Dr. Marshall lab for their help and a great time we spent together. In particular, I want to thank Dr. Huan He, Dr. Amy McKenna, Dr. Nathan Kaiser, and Dr. Joshua Savory. I would also like to thank my parents and two elder sisters. They were always supporting me and encouraging me with their best wishes. Finally, I would like to thank my wife, sweet daughter and son, for their firm and continuous love and support. This work was supported by NSF Division of Materials Research through DMR-0654118 and the State of Florida. iv TABLE OF CONTENTS List of Figures.............................................................................................................................. viii Abstract........................................................................................................................................ xiv 1. HIGH RESOLUTION MASS SPECTROMETRY............................................... 1 What Defines High Resolution and High Mass Accuracy………………………………... 1 Mass Resolution and Accuracy………………………………………………………….... 2 Time-of-Flight Mass Analyzers…………………………………………………………... 3 Orthogonal Acceleration………………………………………………………….. 3 Reflectron/Multipass TOF………………………………………………………... 5 Recent Advances in TOF Mass Analyzer……………………………………….... 6 Selected Applications………………………………………………………….......7 Fourier Transform Mass Analyzers…………………………………………………......... 8 Common Features of Fourier Transform Mass Analyzers………………………...9 Ion Accumulation and Detection………………………………………………....10 Advances in Fourier Transform Mass Analyzers ...……………………………...10 SelectedApplications………………………………………………...............….. 17 2. AUTOMATED BROADBAND PHASE CORRECTION OF FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTRA……….... 24 Introduction…………………………………………………………………………....... 24 Problem………………………………………………………………………….. 24 Prior Solutions…………………………………………………………............... 27 Experimental Methods………………………………………………………………….. 29 Sample Description and Preparation…………………………………………….. 29 Instrumentation: 9.4 Tesla FT-ICR MS……………………………………….... 29 Mass Calibration................................................................................................... 30 Computational Method…………………………………………………………. 31 Choosing the Best Phasing Parameters…………………………………………. 32 Baseline Correction……………………………………………………………. 32 Computational Implementation............................................................................ 33 Results and Discussion..................................................................................................... 35 Absorption-Mode vs. Magnitude-Mode Spectral Display.................................... 35 Mass Accuracy..................................................................................................... 35 Filling Gaps Compositional Assignment............................................................... 37 Baseline Roll and Automated Peak Picking.......................................................... 39 Conclusions....................................................................................................................... 40 v 3. BASELINE CORRECTION OF ABSORPTION-MODE FOURIER TRANSFORM ION CYCLOTRON MASS SPECTRA......................................... 41 Introduction........................................................................................................................ 41 Experimental Methods....................................................................................................... 43 Simulation.............................................................................................................. 43 Sample Description and Preparation...................................................................... 45 APPI Source........................................................................................................... 45 9.4 Tesla FT-ICR MS............................................................................................ 46 Mass Calibration.................................................................................................... 46 Baseline Correction Algorithm.............................................................................. 46 Computational Implementation..............................................................................50 Results and Discussion.......................................................................................................50 Mass Accuracy....................................................................................................... 50 Identified Peaks...................................................................................................... 51 Isotopic Distribution...............................................................................................55 4. EFFECTS OF ZERO-FILLING AND APODIZATION ON FOURIER TRANSFORM ION CYCLOTRON RESONANCE MASS SPECTRAL ACCURACY, RESOLUTION, AND SIGNAL-TO-NOISE RATIO.................... 56 Introduction....................................................................................................................... 56 Experimental Methods...................................................................................................... 57 Sample Description and Preparation..................................................................... 57 Instrumentation...................................................................................................... 57 Mass Calibration.................................................................................................... 58 Data Processing..................................................................................................... 58 Computational Implementation............................................................................. 58 Results and Discussion...................................................................................................... 61 Full Apodization vs. Half Apodization.................................................................. 61 Mass Accuracy....................................................................................................... 65 Signal-to-Noise Ratio............................................................................................. 66 Resolving Power.................................................................................................... 66 5. PHASE SPECTRA OF FOURIER TRNSFORM ION CYCLOTRON RESONANCE MASS SPECTROMETRY............................................................. 67 Introduction........................................................................................................................ 67 Method of Stationary phase............................................................................................... 68 Phase Spectrum.................................................................................................................. 69 Chirp/Sweep Excitation Signal.............................................................................. 69 Detected Signal...................................................................................................... 72 Experimental Methods....................................................................................................... 77 Sample Preparation...............................................................................................