UNIVERSITY OF CALIFORNIA SAN DIEGO Novel techniques and applications in single particle mass spectrometry A dissertation submitted in partial satisfaction of the requirements for the degree Doctor of Philosophy in Chemistry by John Francis Cahill Committee in Charge: Professor Kimberly Prather, Chair Professor Lihini Aluwihare Professor Timothy Bertram Professor Robert Continetti Professor James Whitesell 2014 Copyright John Francis Cahill, 2014 All rights reserved. SIGNATURE PAGE The Dissertation of John Francis Cahill is approved, and it is acceptable in quality and form for publication on microfilm and electronically Chair University of California, San Diego 2014 iii DEDICATION To my family and friends who make everything worthwhile iv EPIGRAPH “Shoot for the moon, even if you miss you’ll land among the stars” -Les Brown “Statistics are like a bikini, they show a lot but not everything” -Lou Piniella v TABLE OF CONTENTS SIGNATURE PAGE ..................................................................................................... iii DEDICATION .............................................................................................................. iv EPIGRAPH ..................................................................................................................... v TABLE OF CONTENTS .............................................................................................. vi LIST OF ABBREVIATIONS ...................................................................................... xv LIST OF FIGURES ..................................................................................................... xxi LIST OF SCHEMES ............................................................................................... xxxiv LIST OF TABLES ................................................................................................... xxxv ACKNOWLEDGEMENTS ................................................................................... xxxvii VITA ............................................................................................................................ xlii ABSTRACT OF THE DISSERTATION .................................................................... xlv Chapter 1. Introduction ................................................................................................... 1 1.1 Aerosol background and measurement ................................................................ 1 1.1.1 Metal Organic Frameworks (MOFs) ............................................................. 2 1.1.2 Atmospheric Aerosols ................................................................................... 3 1.1.3 Single cell metabolomics ............................................................................... 5 1.2 Aerosol Instrumentation ....................................................................................... 7 1.2.1 Aerosol time of flight mass spectrometer (ATOFMS) .................................. 7 1.2.2 Particle Sizing Instrumentation ................................................................... 10 1.3 Synopsis of Dissertation ..................................................................................... 11 1.4 References .......................................................................................................... 13 Chapter 2. Postsynthetic modification at orthogonal reactive sites on mixed bifunctional metal-organic frameworks ....................................................................... 20 2.1 Abstract ............................................................................................................... 20 2.2 Introduction ........................................................................................................ 20 2.3 Results ................................................................................................................ 23 2.4 Acknowledgements ............................................................................................ 29 2.5 Supporting information ...................................................................................... 30 vi 2.5.1 General Methods for Metal-Organic Frameworks Experiments. ................ 40 2.5.2 General Methods for Aerosol Time-of-Flight Mass Spectrometry Experiments. ......................................................................................................... 40 2.5.3 Experimental Procedure for Dry Aerosol Generation. ................................ 41 2.5.4 Experimental Procedures for MOFs Synthesis. ........................................... 42 2.5.5 Experimental Procedures for Postsynthetic Modification ........................... 42 2.6 References .......................................................................................................... 45 Chapter 3. Postsynthetic ligand exchange as a route to functionalization of ‘inert’ metal-organic frameworks ............................................................................................ 48 3.1 Abstract ............................................................................................................... 48 3.2 Introduction ........................................................................................................ 48 3.3 Results and Discussion ....................................................................................... 51 3.3.1 ATOFMS on microcrystalline MOFs .......................................................... 51 3.3.2 Ligand exchange between UiO-66-NH2 and UiO-66-Br ............................ 53 3.3.3 Postsynthetic ligand exchange from the liquid phase .................................. 58 3.3.4 Postsynthetic exchange functionalization .................................................... 60 3.4 Conclusions ........................................................................................................ 62 3.5 Acknowledgements ............................................................................................ 63 3.6 Supporting information ...................................................................................... 64 3.6.1 General Methods for Metal-Organic Frameworks Experiments. ................ 75 3.6.2 General Methods for Aerosol Time-of-Flight Mass Spectrometry Experiments. ......................................................................................................... 75 3.6.3 Experimental Procedures for Ligands Synthesis. ........................................ 76 3.6.4 Experimental Procedures for MOFs Exchange. .......................................... 79 3.6.5 Experimental Procedure for Dry Aerosol Generation. ................................ 85 3.6.6 Hierarchical Clustering (HC) Analysis ....................................................... 86 3.6.7 ATOFMS Size Distributions ....................................................................... 86 3.7 References .......................................................................................................... 91 Chapter 4. Postsynthetic Ligand and Ion Exchange in Robust Metal−Organic Frameworks .................................................................................................................. 96 4.1 Abstract ............................................................................................................... 96 vii 4.2 Introduction ........................................................................................................ 97 4.3 Results and Discussion ..................................................................................... 100 4.3.1 Ligand PSE with Robust MOFs. ............................................................... 100 4.3.2 Metal Ion PSE with Robust MOFs. ........................................................... 106 4.3.3 Exploring PSE in Rigorously Separated Samples. .................................... 112 4.4 Conclusion ........................................................................................................ 115 4.5 Acknowledgement ............................................................................................ 116 4.6 Supporting information .................................................................................... 117 4.6.1 General Methods ....................................................................................... 117 4.6.2 Aerosol Time-of-Flight Mass Spectrometry (ATOFMS) .......................... 117 4.6.3 Experimental Procedures for PSE ............................................................. 120 4.7 References ........................................................................................................ 137 Chapter 5. Characterization of core-shell MOF particles by depth profiling experiments using on-line single particle mass spectrometry .................................... 142 5.1 Abstract ............................................................................................................. 142 5.2 Introduction ...................................................................................................... 142 5.3 Experimental ..................................................................................................... 144 5.3.1 ATOFMS ................................................................................................... 144 5.3.2 Preparation of nanomaterials ..................................................................... 145 5.4 Results .............................................................................................................