Abstract
A method is presented to test whether the conversion of the mass spectrum of a polydisperse analyte to its molecular mass distribution is quantitative. Mixtures of samples with different average molecular masses, coupled with a Taylor’s expansion mathematical formalism, were used to ascertain the reliability of molecular mass distributions derived from mass spectra. Additionally, the method describes how the molecular mass distributions may be corrected if the degree of mass bias is within certain defined limits. This method was demonstrated on polydisperse samples of C60 fullerenes functionalized with ethylpyrrolidine groups measured by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry; however, it is applicable to any polydisperse analyte and mass spectrometric method as long as spectrum resolution allows individual oligomers to be identified. Mass spectra of the derivatized fullerenes taken in positive ion mode were shown to give an accurate measurement of the molecular mass distribution while those taken in negative ion mode were not. Differences in the mechanisms for ion formation are used to explain the discrepancy.
Official contribution of the National Institute of Standards and Technology; not subject to copyright in the United States of America.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
McLafferty, F. W.; Turecček, F. Interpretation of Mass Spectra 4th ed.; University Science Books: Sausalito, CA, 1993, p 12.
Guttman, C. M.; Flynn, K. M.; Wallace, W. E.; Kearsley, A. J. A Report on the Certification of an Absolute Molecular Mass Distribution Polymer Standard: Standard Reference Material 2881; NIST Internal Report 7512, National Institute of Standards and Technology: Gaithersburg, MD, 2008. To download a copy, go to http://nvl.nist.gov/pub/nistpubs/ir/2008/ir7512.pdf.
Guttman, C. M.; Flynn, K. M.; Wallace, W. E.; Kearsley, A. J. Quantitative Mass Spectrometry and Polydisperse Materials: Creation of an Absolute Molecular Mass Distribution Polymer Standard. Macromolecules 2009, 42, 1695–1702.
Hirsch, A.; Brettreich, M. Fullerenes—Chemistry and Reactions; Wiley-VCH: Weinheim, 2004.
Martín, N.; Altable, M.; Filippone, S.; Martín-Domenech, A. New Reactions in Fullerene Chemistry. SYNLETT 2007, 20, 3077–3095.
Bausch, J. W.; Surya Prakash, G. K.; Olah, G. A.; Tse, D. S.; Lorents, D. C.; Bae, Y. K.; Malhotra, R. Considered Novel Aromatic Systems: 11. Diamagnetic Polyanions of the C60 and C70 Fullerenes: Preparation, 13C, and 7Li NMR Spectroscopic Observation, and Alkylation with Methyl Iodide to Polymethylated Fullerenes. J. Am. Chem. Soc. 1991, 113, 3205–3206.
Prato, M.; Maggini, M. Fulleropyrrolidines: A Family of Full-Fledged Fullerene Derivatives. Acc. Chem. Res. 1998, 31, 519–526.
Lu, Q.; Schuster, D. I.; Wilson, S. R. Preparation and Characterization of Six bis(N-methylpyrrolidine)-C-60 Isomers: Magnetic Deshielding in Isomeric Bis adducts of C-60. J. Org. Chem. 1996, 61, 4764–4768.
Kordatos, K.; Da Ros, T.; Bosi, S.; Vazquez, E.; Bergamin, M.; Cusan, C.; Pellarini, F.; Tomberli, V.; Baiti, B.; Pantarotto, D.; Georgakilas, V.; Spalluto, G.; Prato, M. Novel Versatile Fullerene Synthons. J. Org. Chem. 2001, 66, 4915–4920.
Wallace, W. E.; Guttman, C. M.; Antonucci, J. M. Molecular Structure of Silsesquioxanes Determined by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1999, 10, 224–230.
Hanton, S. D.; Hyder, I. Z.; Stets, J. R.; Owens, K. G.; Blair, W. R.; Guttman, C. M.; Giuseppetti, A. A. Investigations of Electrospray Sample Deposition for Polymer MALDI Mass Spectrometry. J. Am. Soc. Mass Spectrom. 2004, 15, 168–179.
Wallace, W. E.; Flynn, K. M.; Guttman, C. M.; VanderHart, D. L.; Prabhu, V. M.; De Silva, A.; Felix, N. M.; Ober, C. K. Quantitative Measurement of the Polydispersity in the Extent of Functionalization of Glass Forming Calix[4]Resorcinarenes. Rapid Commun. Mass Spectrom. 2009, DOI: 10.1002/rem.4099.
Brown, T.; Clipston, N. L.; Simjee, N.; Luftmann, H.; Hungerbühler, H.; Drewello, T. Matrix-Assisted Laser Desorption/Ionization of Amphiphilic Fullerene Derivatives. Int. J. Mass Spectrom. 2001, 210/211, 249–263.
Hunter, E. P. L.; Lias, S. G. Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update. J. Phys. Chem. Ref. Data 1998, 27, 413–656.
Brink, C.; Anderson, L. H.; Hvelplund, P.; Mathur, D.; Voldstad, J. D. Laser Photodetachment of C-60(−) and C-70(−) Ions Colled in a Storage Ring. Chem. Phys. Lett. 1995, 233, 52–56.
Guldi, D. M.; Prato, M. Excited-State Properties of C60 Fullerene Derivatives. Acc. Chem. Res. 2000, 33, 695–703.
Sun, Y. P.; Drovetskaya, T.; Bolskar, R. D.; Bau, R.; Boyd, P. D. W.; Reed, C. A. Fullerides of Pyrrolidine-functionalized C-60. J. Org. Chem. 1997, 62, 3642–3649.
Brustolon, M.; Zoleo, A.; Agostini, G.; Maggini, M. Radical Anions of Mono- and Bis-Fulleropyrrolidines: An EPR Study. J. Phys. Chem. A 1998, 102, 6331–6339.
Knochenmuss, R. A Quantitative Model of Ultraviolet Matrix-assisted Laser Desorption/Ionization Including Analyte Ion Generation. Anal. Chem. 2003, 75, 2199–2207.
Streletskii, A. V.; Ioffe, I. N.; Kotsiris, S. G.; Barrow, M. P.; Drewello, T.; Strauss, S. H.; Boltalina, O. V. In Plume Thermodynamics of MALDI Generation of Fluorofullerene Anions. J. Phys. Chem. A 2005, 109, 714–719.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online May 5, 2009
Rights and permissions
About this article
Cite this article
Park, E.S., Wallace, W.E., Guttman, C.M. et al. A general method for quantitative measurement of molecular mass distribution by mass spectrometry. J Am Soc Mass Spectrom 20, 1638–1644 (2009). https://doi.org/10.1016/j.jasms.2009.04.019
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2009.04.019