Matthew F. Bush, Ph.D.

Biography

As an undergraduate, I used resonance enhanced multiphoton ionization and time-of-flight mass spectrometry to study the gas-phase electronic structure metal carbonyls with Professor William E. Hollingsworth at Carleton College, where I received a B.A. in chemistry with a concentration in Environmental and Technology Studies. I received my Ph.D. in chemistry with Professor Evan R. Williams and Professor Richard J. Saykally in the Department of Chemistry at the University of California, Berkeley. My dissertation focused on the use of infrared laser spectroscopy, mass spectrometry, and computational chemistry to study biomolecular and hydrated ions in the gas phase.  

Research Projects

Infrared Spectroscopy and Ion Cyclotron Resonance Mass Spectrometry

Electrospray ionization and ion cyclotron resonance mass spectrometry enable the formation of a wide variety of clusters containing, for example, different amino acids, cations, and solvents.  These clusters can be probed with a variety of technique, such as black body infrared radiative dissociation (BIRD, yields information about ion stability) and infrared photodissociation (yield information about ion structure). 

Zwitterion Formation

The in vivo structure of biomolecules is the result of both intramolecular interactions intrinsic to the molecule and intermolecular interactions with surrounding solvent and neighboring molecules. These effects are each significant and often favor radically different structures. For example, amino acids in aqueous solution are zwitterions over a wide pH range, even though nonzwitterionic structures are energetically favored in the gas phase. Clearly water preferentially stabilizes the zwitterionic form of amino acids. While this general concept is well understood, the full structural impact of water on biomolecular structure remains poorly characterized.  These studies yield detailed information on zwitterion stability and contribute towards a general understanding of zwitterion and salt-bridge formation in biological systems.

Ion Solvation

Free-energy changes for ion binding in biology are controlled by both metal-ligand contacts formed in the complex and the disruption of interactions present in the unbound state.  The first step in understanding these and related problems is to gain a detailed understanding of water coordination to ions and how ions can affect the extended hydrogen bond network in solution.  Infrared spectroscopy and mass spectrometry are powerful probes of hydrated ions and the study of size-selected clusters enables a detailed understanding of solutions, developed one molecule at a time.  Despite serving critical chemical and structural roles in biology, experimental studies of hydrated, multiply charged ions have lagged behind those of singly charged ions due to significant experimental challenges. With this technique, increasing hydration results in spectroscopic signatures indicating the completion of the first solvation shells of multiply charge ions and shows that the effects of these ions can persist through very large clusters.

Publications

• Bush, M. F.; Saykally, R.J.; Williams, E. R. Reactivity and Infrared Spectroscopy of Gaseous Hydrated Trivalent Metal Ions  J. Am. Chem. Soc. 2008, 130, 9122-9128. web
• Bush, M. F.; Oomens, J.; Saykally, R. J.; Williams, E. R. Effects of Alkaline Earth Metal Ion Complexation on Amino Acid Zwitterion Stability: Results from Infrared Action Spectroscopy. J. Am. Chem. Soc. 2008, 130, 6463-6471. web
• Donald, W. A.; Leib, R. D.; O'Brien, J. T.; Bush, M. F.; Williams, E. R. Absolute Standard Hydrogen Electrode Potential Measured by Reduction of Aqueous Nanodrops in the Gas Phase. J. Am. Chem. Soc. 2008, 130, 3371-3381. web
• Forbes, M. W.; Bush, M. F.; Polfer, N. C; Oomens, J.; Dunbar, R. C.; Williams, E. R.; Jockusch, R. A. Infrared Spectroscopy of Arginine Cation Complexes: Direct Observation of Gas-Phase Zwitterions J. Phys. Chem. A 2007, 111, 11759-11770. web
• Bush, M. F.; Prell, J. S; Saykally, R. J.; Williams, E. R. One Water Molecule Stabilizes the Cationized Arginine Zwitterion J. Am. Chem. Soc. 2007, 129, 13544-13553. web
• Bush, M. F.; Saykally, R.J.; Williams, E. R. Hydration of the Calcium Dication: Direct Evidence for Second Shell Formation from Infrared Spectroscopy ChemPhysChem 2007, 8, 2245 - 2253. web  Cover Article web
• Bush, M. F.; Forbes, M.W.; Jockusch, R.A; Oomens, J.; Polfer, N.C; Saykally, R.J.; Williams, E. R. Infrared Spectroscopy of Cationized Lysine and e-N-methyllysine in the Gas Phase: Effects of Alkali-Metal Ion Size and Proton Affinty on Zwitterion Stability J. Phys. Chem. A  2007, 111, 7753-7760. web
• Leib, R. D.; Donald, W. A.; O'Brien, J. T.; Bush, M. F.; Williams, E. R. Reduction Energy of 1 M Aqueous Ruthenium(III) Hexaammine in the Gas Phase: A Route toward Establishing an Absolute Electrochemical Scale J. Am. Chem. Soc. 2007, 129, 716-7717. web
• Bush, M. F., Saykally, R. J. and Williams, E. R. Evidence for Water Rings in the Hexahydrated Sulfate Dianion from IR Spectroscopy J. Am. Chem. Soc. 2007, 129, 2220-2221.  web
• Leib, R. D.; Donald, W. A.; Bush, M. F.; O'Brien, J. T.; Williams, E. R. Nonergodicity in Electron Capture Dissociation Investigated Using Hydrated Ion Nanocalorimetry J. Am. Soc. Mass Spectrom. 2007, 18, 1217-1231. web
• Leib, R. D.; Donald, W. A.; Bush, M. F.; O'Brien, J. T.; Williams, E. R. Internal Energy Deposition in Electron Capture Dissociation Measured Using Hydrated Divalent Metal Ions as Nanocalorimeters J. Am. Chem. Soc. 2007, 129, 4894-4895. web
• Bush, M. F., O'Brien, J. T., Prell, J. S., Saykally, R. J. and Williams, E. R. Infrared Spectroscopy of Cationized Arginine in the Gas Phase: Direct Evidence for the Transition from Nonzwitterionic to Zwitterionic Structure J. .Am. Chem. Soc. 2007, 129, 1612-1622. web  One of the 10 Most-Cited J. Am. Chem. Soc. publications in 2007  web 
• Bush, M. F., Saykally, R. J. and Williams, E. R. Formation of Hydrated Triply Charged Metal Ions from Aqueous Solutions using Nanodrop Mass Spectrometry Int. J. Mass Spectrom. 2006, 252, 256-262. web
• Kamariotis, A., Boyarkin, O. V., Mercier, S., Beck, R. D., Bush, M. F., Williams, E. R. and Rizzo, T. R.. Infrared Spectroscopy of hydrated amino acids in the gas phase: protonated and lithiated valine J. Am. Chem. Soc. 2006, 128, 905-916. web
• Lemoff, A. S., Bush, M. F., O'Brien, J. T. and Williams, E. R. Structures of Lithiated Lysine and Structural Analogues in the Gas Phase: Effects of Water and Proton Affinity on Zwitterionic Stability J. Phys. Chem. A 2006, 110, 8433-8442. web
• Lemoff, A. S., Wu, C.-C., Bush, M. F. and Williams, E. R.. Binding Energies of Water to Doubly Hydrated Cationized Glutamine and Structural Analogues in the Gas Phase J. Phys. Chem. A 2006, 110, 3662-3669. web
• Lemoff, A. S., Bush, M. F., Wu, C. C. and Williams, E. R.. Structures and hydration enthalpies of cationized glutamine and structural analogues in the gas phase J. Am. Chem. Soc. 2005, 127, 10276-10286. web
• Lemoff, A. S., Bush, M. F. and Williams, E. R.. Structures of Cationized Proline Analogues: Evidence for the Zwitterion Form J. Phys. Chem. A 2005, 109, 1903-1910. web
• Williams, E. R., Jurchen, J. C., Garcia, D. E., Lemoff, A. S. and Bush, M. F.. Noncovalent Biomolecule Complexes Both Large and Small Advances in Mass Spectrometry. 2004, 16, 79-94.
• Lemoff, A. S., Bush, M. F. and Williams, E. R.. Binding energies of water to sodiated valine and structural isomers in the gas phase: The effect of proton affinity on zwitterion stability J. Am. Chem. Soc. 2003, 125, 13576-13584. web

Talks

• Matthew F. Bush, Richard J. Saykally & Evan R. Williams Infrared Action Spectroscopy of Hydrated Multiply Charged Ions in the Gas Phase 56th American Society for Mass Spectrometry Conference, Denver, CO June, 2008.
• Matthew F. Bush, Richard J. Saykally & Evan R. Williams Zwitterions in the Gas Phase: Results from IR Spectroscopy of Electrospray Generated Ions Western Spectroscopy Association Conference, Pacific Grove, CA February, 2008.
• Matthew F. Bush, Richard J. Saykally & Evan R. Williams Formation, Dissociation, and Infrared Spectroscopy of Hydrated Trivalent Metal Ions Lake Arrowhead Ion Chemistry Conference, Lake Arrowhead, CA January, 2008.
• Matthew F. Bush, Jeremy T. O'Brien, James S. Prell, Richard J. Saykally & Evan R. Williams Infrared Spectroscopy of Biomolecular and Hydrated Ions Lake Arrowhead Ion Chemistry Conference, Lake Arrowhead, CA January, 2007.
• Matthew F. Bush, Jeremy T. O'Brien, Chih-Che Wu, Richard J. Saykally & Evan R. Williams Spectroscopy of Hydrated Clusters Formed by Electrospray Ionization Western Spectroscopy Association Conference, Pacific Grove, CA February, 2006.
• Matthew F. Bush, Jeremy T. O'Brien, Chih-Che Wu, Richard J. Saykally & Evan R. Williams Vibrational Spectroscopy of Hydrated Divalent Metal Ions Formed by Electrospray Ionization Lake Arrowhead Ion Chemistry Conference, Lake Arrowhead, CA January, 2006.
• Matthew F. Bush, Andrew S. Lemoff & Evan R. Williams Hydrated Clusters of Amino Acids: Evidence for Gas-Phase Zwitterions Lake Arrowhead Ion Chemistry Conference. January, 2004.

Posters

• Matthew F. Bush, Jos Oomens, Richard J. Saykally & Evan R. Williams Effects of Alkaline Earth Metal Complexation on Amino Acid Zwitterion Stability: Results from Infrared Action Spectroscopy Lake Arrowhead Ion Chemistry Conference, Lake Arrowhead, CA January, 2008.
• Matthew F. Bush, Jeremy T. O'Brien, James S. Prell, Matthew Forbes, Nick C. Polfer, Jos Oomens, Rebecca A. Jockusch, Richard J. Saykally, & Evan R. Williams Spectroscopy of Biomolecular and Hydrated Ions  Gordon Research Conference on Gaseous Ions, Ventura, CA February, 2007.
• Matthew F. Bush, Jeremy T. O'Brien, Chih-Che Wu, Richard J. Saykally, & Evan R. Williams Spectroscopy of Electrospray Generated Ions  Gordon Research Conference on Biomolecules in the Gas Phase, Lewiston, ME July, 2005.
• Andrew S. Lemoff, Matthew F. Bush & Evan R. Williams Binding Energy of Water to Cationized Amino Acids: Formation of Gas-Phase Zwitterions American Society for Mass Spectrometry Annual Conference, Montreal, Quebec June, 2003.
• Matthew F. Bush, Andrew S. Lemoff & Evan R. Williams Zwitterions, Salt Bridges, and the Role of Solvent 225th ACS National Meeting, New Orleans, LA 2003.

Professional Experience

• Postdoctoral Chair for planned 2009 Gordon Research Seminar on Biological Molecules in the Gas Phase.
• Member, American Chemical Society
• Member, American Society for Mass Spectrometry
• Member, Bay Area Mass Spectrometry Society
  

Teaching Experience

• Graduate Student Instructor, Chem 268: Graduate Level Mass Spectrometry. Fall 2005. 
• Graduate Student Instructor, Chem 105: Instrumental Methods in Analytical Chemistry. Fall 2004. 
• Graduate Student Instructor, Chem 1A: Introduction to Chemistry. Fall 2003. 

Awards

• ACS Undergraduate Award in Analytical Chemistry. 2003.
• Hypercube Scholar for Work on Computers in Chemistry. 2003.
• Distinction in major, Department of Chemistry, Carleton College. 2003.
• Distinction in senior integrative exercise, Department of Chemistry, Carleton College. 2002.

Contact Information

mattbush@berkeley.edu

Matthew F. Bush
Williams & Saykally Groups
Department of Chemistry
University of California
Berkeley, CA 94720-1460

Tel: (510) 642-6240
Fax: (510) 642-7714

Site created and maintained by Matthew F. Bush.