Abstract
In this paper, we report negative ion microelectrospray Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry of C60 samples containing ∼1% 3He@C60 or 4He@C60. Resolving 3He@C −60 and 4He@C −60 from C60 containing 3 or 4 13C instead of 12C atoms is technically challenging, because the target species are present in low relative abundance and are very close in mass. Nevertheless, we achieve baseline resolution of 3He@C −60 from 13C 123 C −57 and 4He@C −60 from 13C 124 C −56 in single-scan mass spectra obtained in broadband mode without preisolation of the ions of interest. The results constitute the first direct mass spectrometric observation of endohedral helium in a fullerene sample at this (low) level of incorporation. The results also demonstrate the feasibility of determining the extent of He incorporation from the FT-ICR mass spectral peak heights. The present measurements are in agreement with those obtained by the pyrolysis method [1–3]. Although limited in sensitivity, the mass spectral method is faster and easier than pyrolysis.
Article PDF
Similar content being viewed by others
References
Saunders, M.; Jimenez-Vazquez, H. A.; Cross, R. J.; Poreda, R. J. Stable Compounds of Helium and Neon—He@C60 and Ne@C60. Science 1993, 259, 1428–1430.
Saunders, M.; Jimenez-Vazquez, H. A.; Cross, R. J.; Mroczkowski, S.; Gross, M. L.; Giblin, D. E.; Poreda, R. J. Incorporation of Helium, Neon, Argon, Krytpon, and Xenon into Fullerenes Using High Pressure. J. Am. Chem. Soc. 1994, 116, 2193–2194.
Saunders, M.; Cross, R. J.; Jimenez-Vazquez, H. A.; Shimshi, R.; Khong, A. Noble Gas Atoms Inside Fullerenes. Science 1996, 271, 1693–1697.
Chai, Y.; Guo, T.; Jin, C.; Haufler, R. E.; Chibante, L. P. F.; Fure, J.; Wang, L.; Alford, J. M.; Smalley, R. E. Fullerenes with Metals Inside. J. Phys. Chem. 1991, 95, 7564–7568.
Heath, J. R.; O’Brien, S. C.; Zhang, Q.; Lin, Y.; Curl, R. F.; Kroto, H. W.; Tittel, F. K.; Smalley, R. E. Lanthanum Complexes of Spheroidal Carbon Shells. J. Am. Chem. Soc. 1985, 107, 7779–7780.
Weiss, F. D.; Elkind, J. L.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. Photophysics of Metal Complexes of Spheroidal Carbon Shells. J. Am. Chem. Soc. 1988, 110, 4464–4465.
Kroto, H. W.; Heath, J. R.; O’Brien, S. C.; Curl, R. F.; Smalley, R. E. C-60—Buckminsterfullerene. Nature 1985, 318, 162–163.
Krätschmer, W.; Lamb, L. D.; Fostiropoulos, K.; Huffman, D. R. Solid C-60—A New Form of Carbon. Nature 1990, 347, 354–358.
Weiske, T.; Bohme, D. K.; Hrusak, J.; Krätschmer, W.; Schwarz, H. Endohedral Cluster Compounds—Inclusion of Helium Within C60+· and C70+· Through Collision Experiments. Angew. Chem. Int. Ed. Engl. 1991, 30, 884–886.
Caldwell, K. A.; Giblin, D. E.; Hsu, C.; Cox, D.; Gross, M. L. Endohedral Complexes of Fullerene Radical Cations. J. Am. Chem. Soc. 1991, 113, 8519–8521.
Ross, M.; Callahan, J. H. Formation and Characterization of C60He+. J. Phys. Chem. 1991, 95, 5720–5723.
Weiske, T.; Hrusak, J.; Bohme, D. K.; Schwarz, H. Endohedral Fullerene-Noble Gas Clusters Formed with High Energy Bomolecular Reactions of CxN+ (X = 60, 70; N = 1, 2, 3). Helv. Chim. Acta. 1992, 75, 79–89.
Caldwell, K. A.; Giblin, D. E.; Gross, M. L. High Energy Collisions of Fullerene Radical Cations with Target Gase—Capture of the Target Gas and Charge Stripping of c60+·, C70+·, and C84+·. J. Am. Chem. Soc. 1992, 114, 3743–3756.
Mosely, J. A.; Cooper, H. J.; Gallagher, R. T.; Derrick, P. J. Target Capture of Argon by Fullerene Radical Cations in High-Energy Collisions. Eur. Mass Spectrom. 1995, 1, 501–502.
Tellgmann, R.; Krawez, N.; Lin, S.-H.; Hertel, I. V.; Campbell, E. E. B. Endohedral Fullerene Production. Nature 1996, 382, 407–408.
Wan, Z.; Christian, J. F.; Anderson, S. L. Collision of Li+ and Na+ with C60—Insertion, Fragmentation, and Thermionic Emission. Phys. Rev. Lett. 1992, 69, 1352–1355.
Wan, Z.; Christian, J. F.; Basir, Y.; Anderson, S. L. Collision of Alkali Ions with C60/C70—Insertion, Thermionic Emission, and Fragmentation. J. Chem. Phys. 1993, 99, 5858–5870.
Shimshi, R.; Cross, R. J.; Saunders, M. Beam Implantation: A New Method for Preparing Cage Molecules Containing Atoms at High Incorporation Levels. J. Am. Chem. Soc. 1997, 119, 1163–1164.
Murphy, T. A.; Pawlik, T.; Weidinger, A.; Hohne, M.; Alcala, R.; Spaeth, J. M. Observation of Atomlike Nitrogen in Nitrogen-Implanted Solid C60. Phys. Rev. Lett. 1996, 77, 1075–1078.
DiCamillo, B. A.; Hettich, R. L.; Guiochon, G.; Compton, R. N.; Saunders, M.; Jimenez-Vazquez, H. A.; Khong, A.; Cross, R. J. Enrichment and Characterization of a Noble Gas Fullerene: Ar@C60. J. Phys. Chem. 1996, 100, 9197–9201.
Khong, A.; Jimenez-Vazquez, H. A.; Saunders, M.; Cross, R. J.; Laskin, J.; Peres, T.; Lifshitz, C.; Strongin, R.; Smith, A. B. III. An NMR Study of He2 Inside C70. J. Am. Chem. Soc. 1998, 120, 6380–6383.
Saunders, M.; Jimenez-Vazquez, H. A.; Cross, R. J.; Mroczkowski, S.; Freedburg, D. I.; Anet, F. A. L. Probing the Interior of Fullerenes by He-3-NMR Spectroscopy. Nature 1994, 367, 256–258.
Cross, R. J.; Saunders, M. Catalyzed Incorporation of Noble Gases in Fullerenes. Vol. Fullerenes-XI: Fullerenes for the New Millenium. Proceedings of the 199th Electrochemical Society Conference; Washington, DC, March, 2001; pp 298–300.
Becker, L.; Poreda, R. J.; Bunch, T. E. Fullerenes: An Extraterrestrial Carbon Carrier Phase for Noble Gases. Proc. Natl. Acad. Sci. U.S.A. 2000, 97, 2979–2983.
Shimshi, R.; Khong, A.; Jimenez-Vazquez, H. A.; Cross, R. J.; Saunders, M. Release of Noble Gas Atoms from Inside Fullerenes. Tetrahedron 1996, 52, 5143–5148.
Hendrickson, C. L.; Emmett, M. R. Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Annu. Rev. Phys. Chem. 1999, 50, 517–536.
Smith, R. D.; Loo, J. A. Ogorzalek; Loo, R. R.; Busman, M.; Udseth, H. R. Electrospray MS Review. Mass Spectrom. Rev. 1991, 10, 359–451.
Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Electrospray Ionization for Mass Spectrometry of Large Biomolecules. Science 1989, 246, 64–71.
Marshall, A. G.; Hendrickson, C. L.; Jackson, G. S. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry: A Primer. Mass Spectrom. Rev. 1998, 17, 1–35.
Stults, J. T. Minimizing Peak Coalescence: High Resolution Separation of Isotope Peaks in Partially Deamidated Peptides by Matrix Assisted Laser Desorption/Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Anal. Chem. 1997, 69, 1815–1819.
Solouki, T.; Emmett, M. R.; Guan, S.; Marshall, A. G. Detection, Number, and Sequence Location of Sulfur-Containing Amino Acids and Disulfide Bridges in Peptides by Ultrahigh-Resolution MALDI FTICR Mass Spectrometry. Anal. Chem. 1997, 69, 1163–1168.
Guan, S.; Wahl, M. C.; Marshall, A. G. Elimination of Frequency Drift from FTICR Mass Spectra by Digital Quadrature Heterodyning—Ultrahigh Mass Resolving Power for Laser Desorbed Molecules. Anal. Chem. 1993, 3647–3653.
Wanczek, K.-P. Proceedings of the Pittsburgh Conference on Analytical and Chemical Applications on Spectroscopy; Atlantic City, NJ, 1987; Paper 562.
Beu, S. C.; Senko, M. W.; Quinn, J. P.; Wampler, F. M.; McLafferty, F. W. Fourier Transform ESI Instrumentation for Tandem High Resolution Mass Spectrometry of Large Molecules. J. Am. Soc. Mass Spectrom. 1993, 4, 557–565.
Shi, S. D.-H.; Hendrickson, C. L.; Marshall, A. G. Counting Individual Sulfur Atoms in a Protein by Ultrahigh Resolution FTICR Mass Spectrometry: Experimental Resolution of Isotopic Fine Structure in Proteins. Proc. Natl. Acad. Sci. U.S.A. 1998, 95, 11532–11537.
Mitchell, D. W.; Smith, R. D. Cyclotron Motion of Two Coulombically Interacting Ion Clouds with Implications to FTICR Mass Spectrometry. Phys. Rev. E 1995, 52, 4366–4386.
Mitchell, D. W.; Smith, R. D. Prediction of a Space Charge Induced Upper Molecular Mass Limit Towards Achieving Unit Mass Resolution in FTICR Mass Spectrometry. J. Mass Spectrom. 1996, 31, 771–790.
Pasa-Tolic, L.; Huang, Y.; Guan, S.; Kim, H. S.; Marshall, A. G. Ultrahigh Resolution Matrix-Assisted Laser Desorption Ionization FTICR Mass Spectra of Peptides. J. Mass Spectrom. 1995, 30, 825–833.
Peurrung, A. J.; Kouzes, R. T. Analysis of Space Charge Effects in Cyclotron Resonance Mass Spectrometry as Coupled Gyrator Phenomena. Int. J. Mass Spectrom. Ion Processes 1995, 145, 139–153.
Hsu, C. S.; Liang, Z.; Campana, J. E. Hydrocarbon Characterization by Ultrahigh Resolution FTICR Mass Spectrometry. Anal. Chem. 1994, 66, 850–855.
Kelleher, N. L.; Senko, M. W.; Seigel, M. M.; McLafferty, F. W. Unit Resolution Mass Spectra of 112 kDa Molecules with 3 Da Accuracy. J. Am. Soc. Mass Spectrom. 1997, 8, 380–383.
He, F.; Hendrickson, C. L.; Marshall, A. G. Baseline Mass Resolution of Peptide Isobars: A Record for Molecular Mass Resolution. Anal. Chem. 2001, 73, 647–650.
Guan, S.; Marshall, A. G. Stored Waveform Inverse Fourier Transform (SWIFT) Ion Excitation in Trapped-Ion Mass Spectrometry: Theory and Applications. Int. J. Mass Spectrom. Ion Processes 1996, 157/158, 5–37.
Marshall, A. G.; Wang, T.-C. L.; Ricca, T. L. Tailored Excitation for Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. J. Am. Chem. Soc. 1985, 107, 7893–7897.
Drader, J. J.; Shi, S. D.-H.; Blakney, G. T.; Hendrickson, C. L.; Laude, D. A.; Marshall, A. G. Digital Quadrature Heterodyne Detection for High-Resolution FTICR Mass Spectrometry. Anal. Chem. 1999, 71, 4758–4763.
Jackson, G. S.; White, F. M.; Guan, S.; Marshall, A. G. Matrix-Shimmed Ion Cyclotron Resonance Ion Trap Simultaneously Optimized for Excitation, Detection, Quadrupolar Axialization, and Trapping. J. Am. Soc. Mass Spectrom. 1999, 10, 759–769.
Rempel, D. L.; Gross, M. L. High-Pressure Trapping in FTMS—A Radiofrequency-Only-Mode Event. J. Am. Soc. Mass Spectrom. 1992, 3, 590–594.
Marshall, A. G.; Guan, S. Advantages of High Magnetic Field for FT-ICR Mass Spectrometry. Rapid Commun. Mass Spectrom. 1996, 10, 1819–1823.
Wu, M.; Wei, X.; Qi, L.; Xu, Z. A New Method for Facile and Selective Generation of C60- and C602- in Aqueous Caustic/THF (or DMSO). Tetrahedron Lett. 1996, 37, 7409–7412.
Scott, L. T. personal communication.
Senko, M. W.; Hendrickson, C. L.; Pasa-Tolic, L.; Marto, J. A.; White, F. M.; Guan, S.; Marshall, A. G. Electrospray Ionization FT-ICR Mass Spectrometry at 9.4 Tesla. Rapid Commun. Mass Spectrom. 1996, 10, 1824–1828.
Senko, M. W.; Hendrickson, C. L.; Emmett, M. R.; Shi, S. D.-H.; Marshall, A. G. External Accumulation of Ions for Enhanced Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1997, 8, 970–976.
Emmett, M. R.; White, F. M.; Hendrickson, C. L.; Shi, S. D.-H.; Marshall, A. G. Application of Micro-Electrospray Liquid Chromatography Techniques to FT-ICR MS to Enable High Sensitivity Biological Analysis. J. Am. Soc. Mass Spectrom. 1998, 9, 333–340.
Quinn, J. P.; Emmett, M. R.; Marshall, A. G. A Device for Fabrication of Emitters for Low-Flow Electrospray Ionization. Proceedings of the 46th ASMS Conference on Mass Spectrometry and Allied Topics; Orlando, FL, 1998; pp 1388–1388.
Chowdhury, S. K.; Katta, V.; Chait, B. T. An Electrospray-Ionization Mass Spectrometer with New Features. Rapid Commun. Mass Spectrom. 1990, 4, 81–87.
Beu, S. C.; Laude, D. A., Jr. Open Trapped Ion Cell Geometries for FT/ICR/MS. Int. J. Mass Spectrom. Ion Processes 1992, 112, 215–230.
Malmberg, J. H.; O’Neil, T. M. Pure Electron Plasma, Liquid, and Crystal. Phys. Rev. Lett. 1977, 39, 1333–1336.
Marshall, A. G.; Roe, D. C. Theory of FTICR Mass Spectroscopy—Response to Frequency Sweep Excitation. J. Chem. Phys. 1980, 73, 1581–1590.
Senko, M. W.; Canterbury, J. D.; Guan, S.; Marshall, A. G. A High-Performance Modular Data System for FT-ICR Mass Spectrometry. Rapid Commun. Mass Spectrom. 1996, 10, 1839–1844.
Ledford, E. B., Jr.; Rempel, D. L.; Gross, M. L. Space Charge Effects in Fourier Transform Mass Spectrometry. Mass Calibration. Anal. Chem. 1984, 56, 2744–2748.
Shi, S. D.-H.; Drader, J. J.; Freitas, M. A.; Hendrickson, C. L.; Marshall, A. G. Comparison and Interconversion of the Two Most Common Frequency-to-Mass Calibration Functions for Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Int. J. Mass Spectrom. 2000, 195/196, 591–598.
Blakney, G. T.; van der Rest, G.; Johnson, J. R.; Freitas, M. A.; Drader, J. J.; Shi, S. D.-H.; Hendrickson, C. L.; Kelleher, N. L.; Marshall, A. G. Further Improvements to the MIDAS Data Station for FT-ICR Mass Spectrometry. Proceedings of the 49th ASMS Conference on Mass Spectrometry and Allied Topics; Chicago, IL, 2001; WPM265.
Audi, G.; Wapstra, A. H. The 1995 Update to the Atomic Mass Evaluation. Nuclear Phys. A 1995, 595, 409–425.
Limbach, P. A.; Schweikhard, L.; Cowen, K. A.; McDermott, M. T.; Marshall, A. G.; Coe, J. V. Observation of the Doubly Charged, Gas Phase Fullerene Anions, C 2−60 and C 2−60 . J. Am. Chem. Soc. 1991, 113, 6795–6798.
Hettich, R. L.; Compton, R. N.; Ritchie, R. H. Doubly Charged Negative-Ions of Carbon-60. Phys. Rev. Lett. 1991, 67, 1242–1245.
Author information
Authors and Affiliations
Corresponding author
Additional information
Member of the Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306, USA.
Rights and permissions
About this article
Cite this article
Cooper, H.J., Hendrickson, C.L., Marshall, A.G. et al. Direct detection and quantitation of He@C60 by ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. J. Am. Soc. Spectrom. 13, 1349–1355 (2002). https://doi.org/10.1016/S1044-0305(02)00650-5
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/S1044-0305(02)00650-5