Abstract
Through analyzing mixtures of compounds of known gas-phase basicities, the importance of this property on the secondary ions emitted from a surface under primary ion bombardment is investigated. The aim is to obtain a greater understanding of the ionization mechanisms that occur in secondary ion mass spectrometry (SIMS). The commonly used matrix assisted laser desorption/ionization (MALDI) matrix 2,4,6-trihydroxyacetophenone (THAP) and a range of low molecular weight biomolecules were used to investigate whether analyte/matrix suppression effects that have been observed in analogous MALDI experiments were also present in static-SIMS. The outcome of the experiments demonstrates that strong suppression of the quasi-molecular signal of one molecule in a mixture can occur due to the presence of the other, with the gas-phase basicity of the compounds being a good indicator of the secondary ions detected. It is also demonstrated that the suppression of the quasi-molecular ion signal of a compound in a two-component mixture can be minimized by the inclusion of a third compound of suitable gas-phase basicity.
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Pacholski, M. L.; Cannon, D. M., Jr.; Ewing, A. G.; Winograd, N. Static Time-of-flight Secondary Ion Mass Spectrometry Imaging of Freeze-fractured, Frozen-Hydrated Biological Membranes. Rapid Commun. Mass Spectrom. 1998, 12, 1232–1235.
Todd, P. J.; McMahon, J. M.; Short, R. T.; McCandlish, C. A. Organic SIMS of Biological Tissue. Anal. Chem 1997, 69, 529A-535A.
Davis, N.; Weibel, D. E.; Blenkinsopp, P.; Lockyer, N.; Hill, R.; Vickerman, J. C. Development and Experimental Application of a Gold Liquid Metal Ion Source. Appl. Surf. Sci. 2003, 203/204, 223–227.
Kollmer, F. Cluster Primary Ion Bombardment of Organic Materials. Appl. Surf. Sci. 2004, 231/232, 153–158.
Weibel, D.; Wong, S.; Lockyer, N.; Blenkinsopp, P.; Hill, R.; Vickerman, J. C. A C60 Primary Ion Beam System for Time of Flight Secondary Ion Mass Spectrometry: Its Development and Secondary Ion Yield Characteristics. Anal. Chem. 2003, 75, 1754–1764.
Wu, K. J.; Odom, R. W. Matrix-Enhanced Secondary Ion Mass Spectrometry: A Method for Molecular Analysis of Solid Surfaces. Anal. Chem. 1996, 68, 873–882.
Delcorte, A.; Medard, N.; Bertrand, P. Organic Secondary Ion Mass Spectrometry: Sensitivity Enhancement by Gold Deposition. Anal. Chem. 2002, 74, 4955–4968.
Altelaar, A. F. M.; Van Minner, J.; Jiménez, C. R.; Heeren, R. M. A.; Piersma, S. R. Direct Molecular Imaging of Lymnaea stagnalis Nervous Tissue at Subcellular Spatial Resolution by Mass Spectrometry. Anal. Chem. 2005, 77, 735–741.
Altelaar, A. F. M.; Klinkert, I.; Jalink, K.; de Lange, R. P. J.; Adan, R. A. H.; Heeren, R. M. A.; Piersma, S. R. Gold-Enhanced Biomolecular Surface Imaging of Cells and Tissue by SIMS and MALDI Mass Spectrometry. Anal. Chem. 2006, 78, 734–742.
McDonnell, L. A.; Piersma, S. R.; Maarten Altelaar, A. F.; Todd, H.; Luxembourg, S. L.; Verhaert, P. D. E. M.; Van Minnen, J.; Heeren, R. M. A. Subcellular Imaging Mass Spectrometry of Brain Tissue. J. Mass Spectrom. 2005, 40, 160–168.
Nygren, H.; Malmberg, P.; Kriegeskotte, C.; Arlinghaus, H. F. Bioimaging TOF-SIMS: Localization of Cholesterol in Rat Kidney Sections. FEBS Lett. 2004, 566, 291–293.
Sjoevall, P.; Lausmaa, J.; Johansson, B. Mass Spectrometric Imaging of Lipids in Brain Tissue. Anal. Chem. 2004, 76, 4271–4278.
Touboul, D.; Halgand, F.; Brunelle, A.; Kersting, R.; Tallarek, E.; Hagenhoff, B.; Laprevote, O. Tissue Molecular Ion Imaging by Gold Cluster Ion Bombardment. Anal. Chem. 2004, 76, 1550–1559.
Nygren, H.; Boerner, K.; Hagenhoff, B.; Malmberg, P.; Mansson, J.-E. Localization of Cholesterol, Phosphocholine, and Galactosylceramide in Rat Cerebellar Cortex with Imaging TOF-SIMS Equipped with a Bismuth Cluster Ion Source. Biochim. Biophys. Acta. 2005, 1737, 102–111.
Touboul, D.; Kollmer, F.; Niehuis, E.; Brunelle, A.; Laprevote, O. Improvement of Biological Time-of-Flight-Secondary Ion Mass Spectrometry Imaging with a Bismuth Cluster Ion Source. J. Am. Soc. Mass Spectrom. 2005, 16, 1608–1618.
Wittmaack, K.; Szymczak, W.; Hoheisel, G.; Tuszynski, W. Time-of-Flight Secondary Ion Mass Spectrometry of Matrix-Diluted Oligo- and Polypeptides Bombarded with Slow and Fast Projectiles: Positive and Negative Matrix and Analyte Ion Yields, Background Signals, and Sample Aging. J. Am. Soc. Mass Spectrom. 2000, 11, 553–563.
Adriaensen, L.; Vangaever, F.; Lenaerts, J.; Gijbels, R. Matrix-Enhanced Secondary Ion Mass Spectrometry: The Influence of MALDI Matrices on Molecular Ion Yields of Thin Organic Films. Rapid Commun. Mass Spectrom. 2005, 19, 1017–1024.
Karas, M.; Bachmann, D.; Bahr, U.; Hillenkamp, F. Matrix-Assisted Ultraviolet Laser Desorption of Nonvolatile Compounds. Int. J. Mass Spectrom. Ion Processes 1987, 78, 53–68.
Karas, M.; Hillenkamp, F. Laser Desorption Ionization of Proteins with Molecular Masses Exceeding 10, 000 Daltons. Anal. Chem. 1988, 60, 2299–2301.
Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida, Y.; Yoshida, T. Protein and Polymer Analysis up to m/z 100,000 by Laser ionization time of flight mass spectrometry. Rapid Commun. Mass Spectrom. 1988, 2, 151–153.
Zenobi, R.; Knochenmuss, R. Ion formation in MALDI mass spectrometry. Mass Spectrom. Rev. 1998, 17, 337–366.
Knochenmuss, R.; Zenobi, R. MALDI Ionization: The Role of in Plume Processes. Chem. Rev. 2003, 103, 441–452.
Breuker, K.; Knochenmuss, R.; Zhang, J.; Stortelder, A.; Zenobi, R. Thermodynamic Control of Final Ion Distributions in MALDI: In-Plume Proton Transfer Reactions. Int. J. Mass Spectrom. 2003, 226, 211–222.
Vickerman, J. C.; Briggs, D., Eds. In: TOF-SIMS: Surface Analysis by Mass Spectrometry; IM Publications and Surface Spectra Limited: Charlton, Chichester, West Sussex, UK, 2001; pp 1–21.
Wucher, A.; Sun, S.; Szakal, C.; Winograd, N. Molecular Depth: Profiling of Histamine in Ice Using a Buckminsterfullerene Probe. Anal. Chem. 2004, 76, 7234–7242.
Kampmeier, J.; Dreisewerd, K.; Schurenberg, M.; Strupat, K. Investigations of 2,5-DHB and succinic acid as matrices for IR and UV MALDI: Part 1. UV and IR ablation in the MALDI process. Int. J. Mass Spectrom. Ion Processes 1997, 169/170, 31–41.
Garrison, B. J. Atoms, Clusters, and Photons: Energetic Probes from Mass Spectrometry. Appl. Surf. Sci. 2006, 252, 6409–6412.
Benninghoven, A. Some Aspects of Secondary Ion Mass Spectrometry of Organic Compounds. Int. J. Mass Spectrom. Ion Phys. 1983, 53, 85–99.
Li, J. X.; Gardella, J. A., Jr.; McKeown, P. J. A Quantitative Time-of-Flight Secondary Ion Mass Spectrometry Study of Ion Formation Mechanisms Using Acid-Base Alternating Langmuir-Blodgett Films. Appl. Surf. Sci. 1995, 90, 205–215.
Cooks, R. G.; Busch, K. L. Matrix Effects, Internal Energies, and MS/MS Spectra of Molecular Ions Sputtered from Surfaces. Int. J. Mass Spectrom. Ion Phys. 1983, 53, 111–124.
Detter, L. D.; Hand, O. W.; Cooks, G.; Walton, R. A. Interfacial Chemical Reactions Accompanying Desorption Ionization Mass Spectrometry. Mass Spectrom. Rev. 1988, 7, 465–502.
Sunner, J. A.; Kulatunga, R.; Kerbarle, P. Fast Atom Bombardment and Gas-Phase Basicities. Anal. Chem. 1986, 58, 1312–1316.
Braun, R. M.; Blenkinsopp, P.; Mullock, S. J.; Corlett, C.; Willey, K. F.; Vickerman, J. C.; Winograd, N. Performance Characteristics of a Chemical Imaging Time-of-Flight Mass Spectrometer. Rapid Commun. Mass Spectrom. 1998, 12, 1246–1252.
Hunter, E. P. L.; Lias, E. G. Evaluated Gas-Phase Basicities and Proton Affinities of Molecules: An Update. J. Phys. Chem. Ref. Data 1998, 27, 413–656.
Russo, N.; Toscano, M.; Grand, A.; Jolibois, F. Protonation of Thymine, Cytosine, Adenine, and Guanine DNA Nucleic Acid Bases; Theoretical Investigation into the Framework of Density Functional Theory. J. Comput. Chem. 1998, 19, 989–1000.
Alvares, E. J.; Brodbelt, J. S. Comparison of the Gas-Phase Basicities and Relative Methylation Nucleophilicities of Carbonyl-Containing Compounds. J. Mass Spectrom. 1996, 31, 901–907.
Benninghoven, A. Static-SIMS Applications—From Silicon Single Crystal Oxidation to DNA Sequencing. J. Vac. Sci. Technol. 1985, 3, 451–460.
Novak, F. P.; Balasanmugan, K.; Viswanadham, K.; Parker, C. D.; Wilk, Z. A.; Mattern, D.; Hercules, D. M. Laser Induced Mass Spectrometry: Ion Formation Processes and Recent Developments. Int. J. Mass Spectrom. Ion Phys. 1983, 53, 135–149.
Inchaouh, J.; Blais, J. C.; Bolbach, G.; Brunot, A. Protonation in Organic Secondary Ion Mass Spectrometry: Correlation with Solution Chemistry Involved in Sample Preparation. Int. J. Mass Spectrom. Ion Processes 1984, 61, 153–156.
Pachuta, S. J.; Cooks, R. G. Mechanisms in Molecular SIMS. Chem. Rev. 1987, 87, 647–669.
Jones, E. A.; Lockyer, N. P.; Vickerman, J. C. Mass Spectral Analysis and Imaging of Tissue by TOF-SIMS—The Role of Buckminsterfullerene C60+ primary ions. Int. J. Mass Spectrom. 2007, 260, 146–157.
Stoeckli, M.; Staab, D.; Schweitzer, A. Compound and Metabolite Distribution Measured by MALDI Mass Spectrometric Imaging in Whole-Body Tissue Sections. Int. J. Mass Spectrom. 2007, 260, 195–202.
Conlan, X. A.; Lockyer, N. P.; Vickerman, J. C. Is Proton Cationization Promoted by Polyatomic Primary Ion Bombardment During Time-of-Flight Secondary Ion Mass Spectrometry Analysis of Frozen Aqueous Solutions? Rapid Commun. Mass Spectrom. 2006, 20, 1327–1334.
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Published online May 24, 2007
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Jones, E.A., Lockyer, N.P., Kordys, J. et al. Suppression and enhancement of secondary ion formation due to the chemical environment in static-secondary ion mass spectrometry. J Am Soc Mass Spectrom 18, 1559–1567 (2007). https://doi.org/10.1016/j.jasms.2007.05.014
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DOI: https://doi.org/10.1016/j.jasms.2007.05.014