Advantages of Monodisperse and Chemically Robust “SpheriCal” Polyester Dendrimers as a “Universal” MS Calibrant

  • Scott M. Grayson
  • Brittany K. Myers
  • Jonas Bengtsson
  • Michael Malkoch
Research Article


The utilization of dendrimer calibrants as an alternative to peptides and proteins for high mass calibration is explored. These synthetic macromolecules exhibited a number of attractive advantages, including exceptional shelf-lives, broad compatibility with a wide range of matrices and solvents, and evenly spaced calibration masses across the mass range examined, 700–30,000 u. The exceptional purity of these dendrimers and the technical simplicity of this calibration platform validate their broad relevance for high molecular weight mass spectrometry.

Key words

Calibrant Dendrimer Calibration Polymer MALDI-TOF MS 

Supplementary material

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  1. 1.
    Vestal, M.L.: The future of biological mass spectrometry. J. Am. Soc. Mass Spectrom. 22, 953–959 (2011)CrossRefGoogle Scholar
  2. 2.
    Steen, H., Mann, M.: The ABC’s (and the XYZ’s) of peptide sequencing. Nature Rev. Mol. Cell Bio. 5, 699–711 (2004)CrossRefGoogle Scholar
  3. 3.
    Montaudo, G., Samperi, F., Montaudo, M.S.: Characterization of synthetic polymers by MALDI-MS. Prog. Polym. Sci. 31, 277–357 (2006)CrossRefGoogle Scholar
  4. 4.
    Gruendling, T., Weidner, S., Falkenhagen, J., Barner-Kowollik, C.: Mass spectrometry in polymer chemistry: a state-of-the-art up-date. Polym. Chem. 1, 599–617 (2010)CrossRefGoogle Scholar
  5. 5.
    Trimpin, S., Weidner, S.M.: Mass spectrometry of synthetic polymers. Anal. Chem. 80, 4349–4361 (2008)CrossRefGoogle Scholar
  6. 6.
    Ihre, H., Padilla de Jesus, O.L., Frechet, J.M.J.: Fast and convenient divergent synthesis of aliphatic ester dendrimers by anhydride coupling. J. Am. Chem. Soc. 123, 5908–5917 (2001)CrossRefGoogle Scholar
  7. 7.
    Peterson, J., Allikmaa, V., Subbi, J., Pehk, T., Lopp, M.: Structural deviations in poly(amidoamine) dendrimers: a MALDI-TOF MS analysis. Eur. Polym. J. 39, 33–42 (2003)CrossRefGoogle Scholar
  8. 8.
    Carlmark, A., Malmström, E., Malkoch, M.: Dendritic architectures based on bis-MPA: functional polymeric scaffolds for application-driven research. Chem. Soc. Rev. 42, 5858–5879 (2013)CrossRefGoogle Scholar
  9. 9.
    Feliu, N., Walter, M.V., Montañez, M.I., Kunzmann, A., Hult, A., Nyström, A., Malkoch, M., Fadeel, B.: Stability and biocompatibility of a library of polyester dendrimers in comparison to polyamidoamine dendrimers. Biomaterials 33, 1970–1981 (2012)CrossRefGoogle Scholar
  10. 10.
    McEwen, C.N., Larsen, B.S.: Accurate mass measurement of proteins using electrospray ionization on a magnetic sector instrument. Rapid Commun. Mass Spectrom. 6, 173–178 (1992)CrossRefGoogle Scholar
  11. 11.
    Cody, R.B., Tamura, J., Musselman, B.D.: Electrospray ionization/magnetic sector mass spectrometry: Calibration, resolution, and accurate mass measurements. Anal. Chem. 64, 1561–1570 (1992)CrossRefGoogle Scholar
  12. 12.
    Pleasance, S., Thibault, P., Sim, P.G., Boyd, R.K.: Cesium iodide clusters as mass calibrants in ionspray mass spectrometry. Rapid Commun. Mass Spectrom. 5, 307–308 (1991)CrossRefGoogle Scholar
  13. 13.
    Anacleto, J.F., Pleasance, S., Boyd, R.K.: Calibration of ion spray mass spectra using cluster ions. Org. Mass Spectrom. 27, 660–666 (1992)CrossRefGoogle Scholar
  14. 14.
    Hop, C.E.C.A.: Generation of high molecular weight cluster ions by electrospray ionization: implications for mass calibration. J. Mass Spectrom. 31, 1314–1316 (1996)CrossRefGoogle Scholar
  15. 15.
    Moini, M., Jones, B.L., Rogers, R.M., Jiang, L.: Sodium trifluoroacetate as a tune/calibration compound for positive- and negative-ion electrospray ionization mass spectrometry in the mass range of 100–4000 Da. J. Am. Soc. Mass Spectrom. 9, 977–980 (1998)CrossRefGoogle Scholar
  16. 16.
    Konig, S., Fales, H.M.: Calibration of mass ranges up to m/z 10,000 in electrospray mass spectrometers. J. Am. Soc. Mass Spectrom. 10, 273–276 (1999)CrossRefGoogle Scholar
  17. 17.
    Letzel, M.C., Agena, C., Mattay, J.: Calibration of electrospray mass spectrometers with rccc-2,8,14,20-tetra-n-octyl-5,11,17,23-tetrahydroxyresorc[4]arene in the high mass range up to m/z 6000. Eur. J. Mass Spectrom. 7, 35–38 (2001)CrossRefGoogle Scholar
  18. 18.
    Clowers, B.H., Dodds, E.D., Seipert, R.R., Lebrilla, C.B.: Dual polarity accurate mass calibration for electrospray ionization and matrix assisted laser desorption/ionization mass spectrometry using malto-oligosaccharides. Anal. Biochem. 381, 205–213 (2008)CrossRefGoogle Scholar
  19. 19.
    Lou, X., van Dongen, J.L.J., Meijer, E.W.: Generation of CsI cluster ions for mass calibration in matrix-assisted laser desorption/ionization mass spectrometry. J. Am. Soc. Mass Spectrom. 21, 1223–1226 (2010)CrossRefGoogle Scholar
  20. 20.
    Zaia, J., Annan, R.S., Bieman, K.: The correct molecular weight of myoglobin, a common calibrant for mass spectrometry. Rapid Commun. Mass Spectrom. 6, 32–36 (1992)CrossRefGoogle Scholar
  21. 21.
    Wooley, K.L., Frechet, J.M.J., Hawker, C.J.: Influence of shape on the reactivity and properties of dendritic, hyperbranched, and linear aromatic polyesters. Polymer 35, 4489–4495 (1994)CrossRefGoogle Scholar
  22. 22.
    Black, C., Poile, C., Langley, J., Herniman, J.: The use of pencil lead as a matrix and calibrant for matrix-assisted laser desorption ionization. Rapid Commun. Mass Spectrom. 20, 1053–1060 (2006)CrossRefGoogle Scholar
  23. 23.
    Daniels, R.H., Dikler, S., Li, E., Stacey, C.: Break free of the matrix: sensitive and rapid analysis of small molecules using nanostructured surfaces and LDI-TOF mass spectrometry. J. Assoc. Lab. Automation 13, 314–321 (2008)CrossRefGoogle Scholar
  24. 24.
    Wyatt, M.F., Ding, S., Stein, B.K., Brenton, A.G., Daniels, R.H.: Analysis of various organic and organometallic compounds using nanostructure-assisted laser desorption/ionization time-of-flight mass spectrometry (NALDI-TOFMS). J. Am. Soc. Mass Spectrom. 21, 1256–1259 (2010)CrossRefGoogle Scholar

Copyright information

© American Society for Mass Spectrometry 2013

Authors and Affiliations

  • Scott M. Grayson
    • 1
  • Brittany K. Myers
    • 1
  • Jonas Bengtsson
    • 2
  • Michael Malkoch
    • 2
    • 3
  1. 1.Department of ChemistryTulane UniversityNew OrleansUSA
  2. 2.Polymer Factory Sweden ABStockholmSweden
  3. 3.Department of Fiber and Polymer Technology, School of Chemical Science and EngineeringKTH Royal Institute of TechnologyStockholmSweden

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