Recent Publications
As a graduate student, Prof. Bush investigated zwitterion formation in gas-phase biomolecules and the hydration of biomolecular and multiply charged ions. Although he no longer pursues these interests, related projects continue in the laboratory of Prof. Evan R. Williams.
25. Sulfate Ion Patterns Water at Long Distances Jeremy T. O’Brien, James S. Prell, Matthew F. Bush, Evan R. Williams. J. Am. Chem. Soc. 2010, 132, 8248–8249.
24. Hydration of Alkaline Earth Metal Dications: Effects of Metal Ion Size Determined Using Infrared Action Spectroscopy Matthew F. Bush, Jeremy T. O’Brien, James S. Prell, Chih-Che Wu, Richard J. Saykally, Evan R. Williams. J. Am. Chem. Soc. 2009, 131, 13270–13277.
23. Proton Affinity and Zwitterion Stability: New Results from Infrared Spectroscopy and Theory of Cationized Lysine and Analogues in the Gas Phase Matthew F. Bush, Jos Oomens, Evan R. Williams. J. Phys. Chem. A 2009, 113, 431–438.
22. Infrared Action Spectra of Ca2+(H2O)11–69 Exhibit Spectral Signatures for Condensed-Phase Structures with Increasing Cluster Size Matthew F. Bush, Richard J. Saykally, Evan R. Williams. J. Am. Chem. Soc. 2008, 130, 15482–15489.
21. Alkali Metal Ion Binding to Glutamine and Glutamine Derivatives Investigated by Infrared Action Spectroscopy and Theory Matthew F. Bush, Jos Oomens, Richard J. Saykally, Evan R. Williams. J. Phys. Chem. A 2008,112, 8578–8584.
20. Reactivity and Infrared Spectroscopy of Gaseous Hydrated Trivalent Metal Ions Matthew F. Bush, Richard J. Saykally, Evan R. Williams.J. Am. Chem. Soc. 2008, 130, 9122–9128.
19. Effects of Alkaline Earth Metal Complexation on Amino Acid Zwitterion Stability: Results from Infrared Action Spectroscopy Matthew F. Bush, Jos Oomens, Richard J. Saykally, Evan R. Williams. J. Am. Chem. Soc. 2008, 130, 6463–6471.
18. The Absolute Standard Hydrogen Electrode Potential Measured by Reduction of Aqueous Nanodrops in the Gas Phase William A. Donald, Ryan D. Leib, Jeremy T. O’Brien, Matthew F. Bush, Evan R. Williams. J. Am. Chem. Soc. 2008, 130, 3371–3381.
17. Infrared Spectroscopy of Arginine Cation Complexes: Direct Observation of Gas-phase Zwitterions Matthew W. Forbes, Matthew F. Bush, Nick C. Polfer, Jos Oomens, Robert C. Dunbar, Evan R. Williams, Rebecca A. Jockusch. J. Phys. Chem. A 2007, 111, 11759–11770.
16. One Water Molecule Stabilizes the Cationized Arginine Zwitterion Matthew F. Bush, James S. Prell, Richard J. Saykally, Evan R. Williams. J. Am. Chem. Soc. 2007, 129, 13544–13553.
15. Hydration of the Calcium Dication: Evidence for Second Shell Formation from Infrared Spectroscopy Matthew F. Bush, Richard J. Saykally, Evan R. Williams. ChemPhysChem 2007, 8, 2245–2253. (cover article)
14. Infrared Spectroscopy of Cationized Lysine and e-N-methyl-lysine in the Gas Phase: Effects of Alkali Metal Ion Size and Proton Affinity on Zwitterion Stability Matthew F. Bush, Matthew W. Forbes, Rebecca A. Jockusch, Jos Oomens, Nick C. Polfer, Richard J. Saykally, Evan R. Williams. J. Phys. Chem. A 2007, 111, 7753–7760.
13. Reduction Potential of 1 M Aqueous Ruthenium(III) Hexaamine in the Gas Phase: A Route Towards Establishing an Absolute Electrochemical Potential Ryan D. Leib, William A. Donald, Jeremy T. O’Brien, Matthew F. Bush, Evan R. Williams. J. Am. Chem. Soc. 2007, 129, 7716–7717.
12. Nonergodicity in Electron Capture Dissociation Investigated Using Hydrated Ion Nanocalorimetry Ryan D. Leib, William A. Donald, Matthew F. Bush, Jeremy T. O’Brien, Evan R. Williams. J. Am. Soc. Mass Spectrom. 2007, 18, 1217–1231.
11. Internal Energy Deposition in Electron Capture Dissociation Measured using Hydrated Divalent Metal Ions as Nanocalorimeters Ryan D. Leib, William A. Donald, Matthew F. Bush, Jeremy T. O’Brien, Evan R. Williams. J. Am. Chem. Soc. 2007, 129, 4894–4895.
10. Evidence for Water Rings in the Hexahydrated Sulfate Dianion from IR Spectroscopy Matthew F. Bush, Richard J. Saykally, Evan R. Williams. J. Am. Chem. Soc. 2007, 129, 2220–2221.
9. Infrared Spectroscopy of Cationized Arginine in the Gas Phase: Direct Evidence for the Transition from Nonzwitterionic to Zwitterionic Structure Matthew F. Bush, Jeremy T. O’Brien, James S. Prell, Richard J. Saykally, Evan R. Williams. J. Am. Chem. Soc. 2007, 129, 1612–1622.
8. Structures of Lithiated Lysine and Structural Analogues in the Gas Phase: Effects of Water and Proton Affinity on Zwitterionic Stability Andrew S. Lemoff, Matthew F. Bush, Jeremy T. O’Brien, Evan R. Williams. J. Phys. Chem. A 2006, 110, 8433–8442.
7. Formation of Hydrated Triply Charged Metal Ions from Aqueous Solutions using Nanodrop Mass Spectrometry Matthew F. Bush, Richard J. Saykally, Evan R. Williams. Int. J. Mass Spectrom. 2006, 253, 256–262.
6. Binding Energies of Water to Doubly Hydrated Cationized Glutamine and Structural Analogues in the Gas Phase Andrew S. Lemoff, Chih-Che Wu, Matthew F. Bush, Evan R. Williams. J. Phys. Chem. A 2006,110, 3662–3669.
5. Infrared Spectroscopy of hydrated amino acids in the gas phase: protonated and lithiated valine Anthi Kamariotis, Oleg V. Boyarkin, Sébastien R. Mercier, Rainer D. Beck , Matthew F. Bush, Evan R. Williams, Thomas R. Rizzo. J. Am. Chem. Soc. 2006, 128, 905–916.
4. Structures and hydration enthalpies of cationized glutamine and structural analogues in the gas phase Andrew S. Lemoff, Matthew F. Bush, Chih-Che Wu, Evan R. Williams. J. Am. Chem. Soc. 2005, 127, 10276–10286.
3. Structures of cationized proline analogues: Evidence for the Zwitterionic form Andrew S. Lemoff, Matthew F. Bush, Evan R. Williams.J. Phys. Chem. A 2005, 109, 1903–1910.
2. Noncovalent Biomolecule Complexes Both Large and Small Evan R. Williams, John C. Jurchen, David E. Garcia, Andrew S. Lemoff, Matthew F. Bush. Adv. Mass Spectrom. 2004, 16, 79–94. Request Reprint
1. Binding energies of water to sodiated valine and structural isomers in the gas phase: The effect of proton affinity on zwitterion stability Andrew S. Lemoff, Matthew F. Bush, Chih-Che Wu, Evan R. Williams. J. Am. Chem. Soc. 2003, 125, 13576–13584.







![Click for Article. In solution, half-cell potentials are measured relative to those of other half cells, thereby establishing a ladder of thermochemical values that are referenced to the standard hydrogen electrode (SHE), which is arbitrarily assigned a value of exactly 0 V. Although there has been considerable interest in, and efforts toward, establishing an absolute electrochemical half-cell potential in solution, there is no general consensus regarding the best approach to obtain this value. Here, ion-electron recombination energies resulting from electron capture by gas-phase nanodrops containing individual [M(NH3)6]3+, M = Ru, Co, Os, Cr, and Ir, and Cu2+ ions are obtained from the number of water molecules that are lost from the reduced precursors. These experimental data combined with nanodrop solvation energies estimated from Born theory and solution-phase entropies estimated from limited experimental data provide absolute reduction energies for these redox couples in bulk aqueous solution. A key advantage of this approach is that solvent effects well past two solvent shells, that are difficult to model accurately, are included in these experimental measurements. By evaluating these data relative to known solution-phase reduction potentials, an absolute value for the SHE of 4.2 ± 0.4 V versus a free electron is obtained. Although not achieved here, the uncertainty of this method could potentially be reduced to below 0.1 V, making this an attractive method for establishing an absolute electrochemical scale that bridges solution and gas-phase redox chemistry.](https://i0.wp.com/biophysicalms.org/wp-content/uploads/2011/06/absolutH1.gif?resize=509%2C199&ssl=1)
![Click for Article. The structures of cationized arginine complexes [Arg + M]+, (M = H, Li, Na, K, Rb, Cs, and Ag) and protonated arginine methyl ester [ArgOMe + H]+ have been investigated in the gas phase using calculations and infrared multiple-photon dissociation spectroscopy between 800 and 1900 cm-1 in a Fourier transform ion cyclotron resonance mass spectrometer. The structure of arginine in these complexes depends on the identity of the cation, adopting either a zwitterionic form (in salt-bridge complexes) or a non-zwitterionic form (in charge-solvated complexes). A diagnostic band above 1700 cm-1, assigned to the carbonyl stretch, is observed for [ArgOMe + H]+ and [Arg + M]+, (M = H, Li, and Ag), clearly indicating that Arg in these complexes is non-zwitterionic. In contrast, for the larger alkali-metal cations (K+, Rb+, and Cs+) the measured IR-action spectra indicate that arginine is a zwitterion in these complexes. The measured spectrum for [Arg + Na]+ indicates that it exists predominantly as a salt bridge with zwitterionic Arg; however, a small contribution from a second conformer (most likely a charge-solvated conformer) is also observed. While the silver cation lies between Li+ and Na+ in metal-ligand bond distance, it binds as strongly or even more strongly to oxygen-containing and nitrogen-containing ligands than the smaller Li+. The measured IR-action spectrum of [Arg + Ag]+ clearly indicates only the existence of non-zwitterionic Arg, demonstrating the importance of binding energy in conformational selection. The conformational landscapes of the Arg−cation species have been extensively investigated using a combination of conformational searching and electronic structure theory calculations [MP2/6-311++G(2d,2p)//B3LYP/6-31+G(d,p)]. Computed conformations indicate that Ag+ is di-coordinated to Arg, with the Ag+ chelated by both the N-terminal nitrogen and Nη of the side chain but lacks the strong M+−carbonyl oxygen interaction that is present in the tri-coordinate Li+ and Na+ charge-solvation complexes. Experiment and theory show good agreement; for each ion species investigated, the global-minimum conformer provides a very good match to the measured IR-action spectrum. Infrared action and calculated spectra of cesiated arginine show evidence for the formation of the gas-phase zwitterion.](https://i0.wp.com/biophysicalms.org/wp-content/uploads/2011/11/ArgFELIX2.jpg?resize=350%2C514&ssl=1)






![Click for Article. Whereas isolated SO42- is unstable, hydrated clusters of this dianion have been formed and investigated using a variety of different methods. Several structures of [SO4(H2O)6]2- have been proposed that account for its high stability in the gas phase. Zhou et al. [J. Chem. Phys. 2006, 125, 111102] recently reported infrared spectra of [SO4(H2O)n]2- in the 540−1850 cm-1 region and assigned the spectrum of the hexahydrated ion to a Td symmetry structure in which all six water molecules donate two hydrogen bonds to the sulfate core. Here, an infrared spectrum of this ion in the hydrogen stretch region (2620−3840 cm-1) and B3LYP/AUG-cc-pVDZ calculations indicate that a significant population of these ions correspond to lower symmetry structures containing water rings in which each water molecule donates hydrogen bonds to both the sulfate dianion and a neighboring water molecule. These calculations indicate that inter-water hydrogen bonds are slightly favored over additional solvation of the dianion core. These results demonstrate that the low- and high-frequency infrared spectra of this ion provide complementary information, and the combination can greatly enhance structural elucidation of these hydrated ions.](https://i0.wp.com/biophysicalms.org/wp-content/uploads/2011/06/sulfate.gif?resize=500%2C191&ssl=1)


![Click for article. Forming hydrated clusters containing triply charged metal ions is challenging due to the competing process of dissociation by forming the metal hydroxide with one less net charge and a protonated water molecule. It is demonstrated for the first time that it is possible to form such clusters using a method we call “nanodrop mass spectrometry”. Clusters of the form [M(H2O)n]3+, where M = Ce, Eu, and La, are generated using electrospray ionization and are mass analyzed in a Fourier-transform ion cyclotron resonance mass spectrometer with an ion cell cooled to −140 °C. Clusters containing trivalent La with n ranging from 16 to over 160 can be readily produced. These clusters are stable at this temperature for many seconds, enabling all standard methods to probe structure and reactivity of these unusual species. Photodissociation experiments on extensively hydrated clusters of trivalent lanthanum using resonant infrared radiation indicate that a minimum of 17 water molecules is necessary to stabilize these trivalent clusters under the low-energy ion excitation conditions and long time frame of these experiments. These results indicate that a minimum droplet size of approximately a nanometer is necessary for these trivalent species to survive intact. This suggests that elemental speciation of trivalent metal ions from aqueous solutions should be possible using nanodrop mass spectrometry. Electrospray interface.](https://i0.wp.com/biophysicalms.org/wp-content/uploads/2011/11/ICRsource.jpg?resize=466%2C227&ssl=1)
![Click for Article. We report here infrared spectra of protonated and lithiated valine with varying degrees of hydration in the gas phase and interpret them with the help of DFT calculations at the B3LYP/6-31++G** level. In both the protonated and lithiated species our results clearly indicate that the solvation process is driven first by solvation of the charge site and subsequently by formation of a second solvation shell. The infrared spectra of Val·Li+(H2O)4 and Val·H+(H2O)4 are strikingly similar in the region of the spectrum corresponding to hydrogen-bonded stretches of donor water molecules, suggesting that in both cases similar extended water structures are formed once the charge site is solvated. In the case of the lithiated species, our spectra are consistent with a conformation change of the amino acid backbone from syn to anti accompanied by a change in the lithium binding from a NO coordination to OO coordination configuration upon addition of the third water molecule. This change in the mode of metal ion binding was also observed previously by Williams and Lemoff [J. Am. Soc. Mass Spectrom. 2004, 15, 1014−1024] using blackbody infrared radiative dissociation (BIRD). In contrast to the zwitterion formation inferred from results of the BIRD experiments upon addition of a third water molecule, our spectra, which are a more direct probe of structure, show no evidence for zwitterion formation with the addition of up to four water molecules.](https://i0.wp.com/biophysicalms.org/wp-content/uploads/2011/06/val_ir.gif?resize=500%2C181&ssl=1)



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