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Why do the Abundances of Ions Generated by MALDI Look Thermally Determined?

  • Research Article
  • Published:
Journal of The American Society for Mass Spectrometry

Abstract

In a previous study (J. Mass Spectrom. 48, 299–305, 2013), we observed that the abundance of each ion in a matrix-assisted laser desorption ionization (MALDI) spectrum looked thermally determined. To find out the explanation for the phenomenon, we estimated the ionization efficiency and the reaction quotient (QA) for the autoprotolysis of matrix, M + M → [M + H]+ + [M − H]−, from the temperature-controlled laser desorption ionization spectra of α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB). We also evaluated the equilibrium constants (KA) for the autoprotolysis at various temperatures by quantum chemical calculation. Primary ion formation via various thermal models followed by autoprotolysis-recombination was compatible with the observations. The upper limit of the effective temperature of the plume where autoprotolysis-recombination occurs was estimated by equating QA with the calculated equilibrium constant.

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References

  1. Hillenkamp, F., Peter-Katalinić, J.: MALDI MS. A Practical Guide to Instrumentation, Methods, and Applications. Wiley-VCH, Weinheim (2007)

    Google Scholar 

  2. Tanaka, K., Waki, H., Ido, Y., Akita, S., Yoshida, Y., Yoshida, T.: Protein and Polymer analyses up to m/z 100,000 by laser ionization time-of-flight mass spectroemtry. Rapid Commun. Mass Spectrom. 2, 151–153 (1988)

    Article  CAS  Google Scholar 

  3. Karas, M., Hillenkamp, F.: Laser desorption ionization of proteins with molecular masses exceeding 10,000 Daltons. Anal. Chem. 60, 2299–2301 (1988)

    Article  CAS  Google Scholar 

  4. Trimpin, S., Wang, B., Inutan, E.D., Li, J., Lietz, C.B., Harron, A., Pagnotti, V.S., Sardelis, D., McEwen, C.N.: A mechanism for ionization of nonvolatile compounds in mass spectrometry: considerations from maldi and inlet ionization. J. Am. Soc. Mass Spectrom. 23, 1644–1660 (2012)

    Article  CAS  Google Scholar 

  5. Duncan, M.W., Roder, H., Hunsucker, S.W.: Quantitative matrix-assisted laser desorption/ionization mass spectrometry. Briefings Funct. Genom. Proteom. 7, 355–370 (2008)

    Article  CAS  Google Scholar 

  6. Bae, Y.J., Park, K.M., Kim, M.S.: Reproducibility of temperature-selected mass spectra in matrix-assisted laser desorption ionization of peptides. Anal. Chem. 84, 7107–7111 (2012)

    Article  CAS  Google Scholar 

  7. Ahn, S.H., Park, K.M., Bae, Y.J., Kim, M.S.: Quantitative reproducibility of mass spectra in matrix-assisted laser desorption ionization and unraveling of the mechanism for gas-phase peptide ion formation. J. Mass Spectrom. 48, 299–305 (2013)

    Article  CAS  Google Scholar 

  8. Brown, R.S., Carr, B.L., Lennon, J.J.: Factors that influence the observed fast fragmentation of peptides in matrix-assisted laser desorption. J. Am. Soc. Mass Spectrom. 7, 225–232 (1996)

    Article  CAS  Google Scholar 

  9. Yoon, S.H., Moon, J.H., Kim, M.S.: A Comparative study of in- and post-source decays of peptide and preformed ions in matrix-assisted laser desorption ionization time-of-flight mass spectrometry: effective temperature and matrix effect. J. Am. Soc. Mass Spectrom. 21, 1876–1883 (2010)

    CAS  Google Scholar 

  10. Ahn, S.H., Park, K.M., Bae, Y.J., Kim, M.S.: Efficient methods to generate reproducible mass spectra in matrix-assisted laser desorption ionization of peptides. J. Am. Soc. Mass Spectrom. 24, 868–876 (2013)

    Article  CAS  Google Scholar 

  11. Kinsel, G.R., Yao, D., Yassin, F.H., Marynick, D.S.: Equilibrium conditions in laser-desorbed plumes: thermodynamic properties of α-cyano-4-hydroxycinnamic acid and protonation of amino acids. Eur. J. Mass Spectrom. 12, 359–367 (2006)

    Article  CAS  Google Scholar 

  12. Asakawa, D., Takayama, M.: Cα–C bond cleavage of the peptide backbone in MALDI in-source decay using salicylic acid derivative matrices. J. Am. Soc. Mass Spectrom. 22, 1224–1233 (2011)

    Article  CAS  Google Scholar 

  13. Molin, L., Seraglia, R., Czarnocki, Z., Maurin, J.K., Pluciński, F.A., Traldi, P.: On the primary ionization mechanism(s) in matrix-assisted laser desorption ionization. J. Anal. Methods Chem. 2012, Article ID 161865 (2012)

  14. Yau, P.Y., Chan, T.W.D., Cullis, P.G., Colburn, A.W., Derrick, P.J.: Threshold fluences for production of positive and negative ions in matrix-assisted laser desorption/ionization using liquid and solid matrices. Chem. Phys. Lett. 202, 93–100 (1993)

    Article  CAS  Google Scholar 

  15. Dashtiev, M., Wäfler, E., Röhling, U., Gorshkov, M., Hillenkamp, F., Zenobi, R.: Positive and negative analyte ion yield in matrix-assisted laser desorption/ionization. Int. J. Mass Spectrom. 268, 122–130 (2007)

    Article  CAS  Google Scholar 

  16. Bae, Y.J., Yoon, S.H., Moon, J.H., Kim, M.S.: Optimization of reflectron for kinetic and mechanistic studies with multiplexed multiple tandem (MSn) time-of-flight mass spectrometry. Bull. Korean Chem. Soc. 31, 92–99 (2010)

    Article  CAS  Google Scholar 

  17. Spengler, B.: Post-source decay analysis in matrix-assisted laser desorption/ionization mass spectrometry of biomolecules. J. Mass Spectrom. 32, 1019–1036 (1997)

    Article  CAS  Google Scholar 

  18. Bae, Y.J., Shin, Y.S., Moon, J.H., Kim, M.S.: Degree of ionization in MALDI of peptides: thermal explanation for the gas-phase ion formation. J. Am. Soc. Mass Spectrom. 23, 1326–1335 (2012)

    Article  CAS  Google Scholar 

  19. Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G.A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H.P., Izmaylov, A.F., Bloino, J., Zheng, G., Sonnenberg, J.L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J.A. Jr., Peralta, J.E., Ogliaro, F., Bearpark, M., Heyd, J.J., Brothers, E., Kudin, K.N., Staroverov, V.N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J.C., Iyengar, S.S., Tomasi, J., Cossi, M., Rega, N., Millam, J.M., Klene, M., Knox, J.E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R.E., Yazyev, O., Austin, A.J., Cammi, R., Pomelli, C., Ochterski, J.W., Martin, R.L., Morokuma, K., Zakrzewski, V.G., Voth, G.A., Salvador, P., Dannenberg, J.J., Dapprich, S., Daniels, A.D., Farkas, Ö., Foresman, J.B., Ortiz, J.V., Cioslowski, J., Fox, D.J.: Gaussian 09, revision A. 02, Gaussian, Inc.: Wallingford CT (2009)

  20. Feldhaus, D., Menzel, C., Berkenkamp, S., Hillenkamp, F., Dreisewerd, K.: Influence of the laser fluence in infrared matrix-assisted laser desorption/ionization with a 2.94 μm Er:YAG laser and a flat-top beam profile. J. Mass Spectrom. 35, 1320–1328 (2000)

    Article  CAS  Google Scholar 

  21. Nishikaze, T., Takayama, M.: Disappearance of interfering alkali-metal adducted peaks from matrix-assisted laser desorption/ionization mass spectra of peptides with serine addition to α-cyano-4-hydroxycinnamic acid matrix. Rapid Commun. Mass Spectrom. 21, 3345–3351 (2007)

    Article  CAS  Google Scholar 

  22. Liao, P.-C., Allison, J.: Ionization processes in matrix-assisted laser desorption/ionization mass spectrometry: matrix-dependent formation of [M + H]+ versus [M + Na]+ ions of small peptides and some mechanistic comments. J. Mass Spectrom. 30, 408–423 (1995)

    Article  CAS  Google Scholar 

  23. Park, K.M., Bae, Y.J., Ahn, S.H., Kim, M.S.: A simple method for quantification of peptides and proteins by matrix-assisted laser desorption ionization mass spectrometry. Anal. Chem. 84, 10332–10337 (2012)

    Article  CAS  Google Scholar 

  24. Moon, J.H., Shin, Y.S., Bae, Y.J., Kim, M.S.: Ion yields for some salts in MALDI: mechanism for the gas-phase ion formation from preformed ions. J. Am. Soc. Mass Spectrom. 22, 162–170 (2012)

    Article  Google Scholar 

  25. Zhigilei, L.V., Leveugle, E., Garrison, B.J., Yingling, Y.G., Zeifman, M.I.: Computer simulations of laser ablation of molecular substrates. Chem. Rev. 103, 321–347 (2003)

    Article  CAS  Google Scholar 

  26. Quist, A.P., Huth-Fehre, T., Sundqvist, B.U.R.: Total yield measurements in matrix-assisted laser desorption using a quartz crystal microbalance. Rapid Commun. Mass Spectrom. 8, 149–154 (1994)

    Article  CAS  Google Scholar 

  27. Puretzky, A.A., Geohegan, D.B.: Gas-phase diagnostics and LIF-imaging of 3-hydroxypicolinic acid MALDI-matrix plumes. Chem. Phys. Lett. 286, 425–432 (1998)

    Article  CAS  Google Scholar 

  28. Yassin, F.H., Marynick, D.S.: Computational estimates of the gas-phase acidities of dihydroxybenzoic acid radical cations and their corresponding neutral species. J. Mol. Struct. Theochem. 629, 223–235 (2003)

    Article  CAS  Google Scholar 

  29. Yassin, F.H., Marynick, D.S.: Computational estimates of the gas-phase basicities, proton affinities and ionization potentials of the six isomers of dihydroxybenzoic acid. Mol. Phys. 103, 183–189 (2005)

    Article  CAS  Google Scholar 

  30. Hasted, J.B.: Physics of Atomic Collisions, p. 444. American Elsevier, New York (1972)

    Google Scholar 

  31. Niu, S., Zhang, W., Chait, B.T.: Direct comparison of infrared and ultraviolet wavelength matrix-assisted laser desorption/ionization mass spectrometry of proteins. J. Am. Soc. Mass Spectrom. 9, 1–7 (1998)

    Article  CAS  Google Scholar 

  32. Chen, X., Carroll, J.A., Beavis, R.C.: Near-ultraviolet-induced matrix-assisted laser desorption/ionization as a function of wavelength. J. Am. Soc. Mass Spectrom. 9, 885–891 (1998)

    Article  CAS  Google Scholar 

  33. Liao, P.-C., Allison, J.: Enhanced Detection of Peptides in matrix-assisted laser desorption/ionization mass spectrometry through the use of charge-localized derivatives. J. Mass Spectrom. 30, 511–512 (1995)

    Article  CAS  Google Scholar 

  34. Zhu, Y.F., Lee, K.L., Tang, K., Allman, S.L., Taranenko, N.I., Chen, C.H.: Revisit of MALDI for small proteins. Rapid Commun. Mass Spectrom. 9, 1315–1320 (1995)

    Article  CAS  Google Scholar 

  35. Karas, M., Krüger, R.: Ion Formation in MALDI: the cluster ionization mechanism. Chem. Rev. 103, 427–439 (2003)

    Article  CAS  Google Scholar 

  36. Jaskolla, T.W., Karas, M.: Compelling evidence for lucky survivor and gas phase protonation: the unified MALDI analyte protonation mechanism. J. Am. Soc. Mass Spectrom. 22, 976–988 (2011)

    Article  CAS  Google Scholar 

  37. Land, C.M., Kinsel, G.R.: The mechanism of matrix to analyte proton transfer in clusters of 2,5-dyhydroxybenzoic acid and the tripeptide VPL. J. Am. Soc. Mass Spectrom. 12, 726–731 (2001)

    Article  CAS  Google Scholar 

  38. Knochenmuss, R., Zhigilei, L.V.: Molecular dynamics model of ultraviolet matrix-assisted laser desorption/ionization including ionization process. J. Phys. Chem. B 109, 22947–22957 (2005)

    Article  CAS  Google Scholar 

  39. Karas, M., Bachmann, D., Hillenkamp, F.: Influence of the wave length in high-irradiance ultraviolet laser desorption mass spectrometry of organic molecules. Anal. Chem. 57, 2935–2939 (1985)

    Article  CAS  Google Scholar 

  40. Musapelo, T., Murray, K.K.: Particle formation in ambient MALDI plumes. Anal. Chem. 83, 6601–6608 (2011)

    Article  CAS  Google Scholar 

  41. Asfandiarov, N.L., Pshenichnyuk, S.A., Fokin, A.I., Lukin, V.G., Fal’ko, V.S.: Electron capture negative ion mass spectra of some typical matrix-assisted laser desorption/ionization matrices. Rapid Commun. Mass Spectrom. 16, 1760–1765 (2002)

    Article  CAS  Google Scholar 

  42. Knochenmuss, R.: Ion formation mechanisms in UV-MALDI. Analyst 131, 966–986 (2006)

    Article  CAS  Google Scholar 

  43. Vertes, A., Irinyi, G., Gijbels, R.: Hydrodynamic model of matrix-assisted laser desorption mass spectrometry. Anal. Chem. 65, 2389–2393 (1993)

    Article  CAS  Google Scholar 

  44. Luo, G., Marginean, I., Vertes, A.: Internal energy of ions generated by matrix-assisted laser desorption/ionization. Anal. Chem. 74, 6185–6190 (2002)

    Article  CAS  Google Scholar 

  45. Vertes, A., Luo, G., Ye, L., Chen, Y., Marginean, I.: Laser pulse length dependence of internal energy transfer in UV-MALDI-MS. Appl. Phys. A 79, 823–825 (2004)

    Article  CAS  Google Scholar 

  46. Liang, C.W., Lee, C.H., Lin, Y., Lee, Y.T., Ni, C.K.: MALDI mechanism of dihydroxybenzoic acid isomers: desorption of neutral matrix and analyte. J. Phys. Chem. B 117, 5058–5064 (2013)

    Article  CAS  Google Scholar 

  47. Stimson, E., Truong, O., Richter, W.J., Waterfield, W.D., Burlingame, A.L.: Enhancement of charge remote fragmentation in protonated peptides by high-energy CID MALDI-TOF-MS using “cold” matrices. Int. J. Mass Spectrom. Ion Processes 169/170, 231–240 (1997)

    Article  CAS  Google Scholar 

  48. Trimpin, S., Inutan, E.D.: Matrix Assisted Ionization in Vacuum, a Sensitive and Widely Applicable Ionization Method for Mass Spectrometry. J. Am. Soc. Mass Spectrom. 24, 722–732 (2013)

    Article  CAS  Google Scholar 

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Acknowledgments

The authors acknowledge support for this work by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MEST) (2012054350). J.H.M. thanks the KRIBB research initiative program.

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Authors and Affiliations

  1. Department of Chemistry, Seoul National University, Seoul, 151-747, Korea

    Yong Jin Bae & Myung Soo Kim

  2. Department of Chemistry, Dongguk University-Seoul, Seoul, 100-715, Korea

    Joong Chul Choe

  3. Medical Proteomics Research Center, KRIBB, Daejeon, 305-806, Korea

    Jeong Hee Moon

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  1. Yong Jin Bae
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Correspondence to Myung Soo Kim.

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Bae, Y.J., Choe, J.C., Moon, J.H. et al. Why do the Abundances of Ions Generated by MALDI Look Thermally Determined?. J. Am. Soc. Mass Spectrom. 24, 1807–1815 (2013). https://doi.org/10.1007/s13361-013-0717-7

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