Abstract
The relative stability of RNA duplexes were determined in both solution and gas phase. Solution stability as determined by a spectrophotometric method indicated that the Watson-Crick duplexes were more stable than duplexes containing one GA mismatch or two tandem GA mismatches. Gas phase stability was determined using ESI-MS through variation of the collision energy in an ion trap. Stability curves similar to the melting curves obtained in solution were observed. The relative stability in gas phase differed, however, from that in solution. The duplexes with two tandem GA mismatches were found to be more stable than the Watson-Crick and single GA mismatch duplexes. The different trends observed in solution versus gas phase can be attributed to the primary means of interaction. In solution, stacking is expected to be the dominant interaction mode. In the gas phase, hydrogen bonding is expected to be the dominant interaction mode. Duplexes with tandem GA mismatches have the potential to undergo additional hydrogen bonding relative to the other duplexes which could account for their increased stability in the gas phase.
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Nordhoff, E.; Kirpekar, F.; Roepstorff, P. Mass Spectrometry of Nucleic Acids. Mass Spectrom. Rev. 1996, 15, 67–138.
Loo, J. A. Studying Noncovalent Protein Complexes by Electrospray Ionization Mass Spectrometry. Mass Spectrom. Rev. 1997, 16, 1–23.
Hofstadler, S. A.; Griffey, R. H. Analysis of Noncovalent Complexes of DNA and RNA by Mass Spectrometry. Chem. Rev. 2001, 101, 377–390.
Light-Wahl, K. J.; Springer, D. L.; Winger, B. E.; Edmonds, C. G.; Camp, D. G.; II, Thrall, B. D.; Smith, R. D. Observation of a Small Oligonucleotide Duplex by Electrospray Ionization Mass Spectrometry. J. Am. Chem. Soc. 1993, 115, 803–804.
Ganem, B. Detection of Oligonucleotide Duplex Forms by Ionspray Mass Spectrometry. Tetrahedron Lett. 1993, 34, 1445–1448.
Gale, D. C.; Goodlett, D. R.; Light-Wahl, K. J.; Smith, R. D. Observation of Duplex DNA-Drug Noncovalent Complexes by Electrospray Ionization Mass Spectrometry. J. Am. Chem. Soc. 1994, 116, 6027–6028.
Doktycz, M. J.; Habibi-Goudarzi, S.; McLuckey, S. A. Accumulation and Storage of Ionized Duplex DNA Molecules in a Quadrupole Ion Trap. Anal. Chem. 1994, 66, 3416–3422.
Bayer, E.; Bauer, T.; Schmeer, K.; Bleicher, K.; Maier, M.; Gaus, H. Analysis of Double Stranded Oligonucleotides by Electrospray Mass Spectrometry. Anal. Chem. 1994, 66, 3858–3863.
Ding, J.; Anderegg, R. J. Specific and Nonspecific Dimer Formation in the Electrospray Ionization Mass Spectometry of Oligonucleotides. J. Am. Soc. Mass Spectrom. 1995, 6, 159–164.
Gale, D. C.; Smith, R. D. Characterization of Noncovalent Complexes Formed Between Minor Groove Binding Molecules and Duplex DNA by Electrospray Ionization Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1995, 6, 1154–1164.
Smith, R. D.; Bruce, J. E.; Wu, Q.; Lei, Q. P. New Mass Spectrometric Methods for the Study of Noncovalent Associations of Biopolymers. Chem. Soc. Rev. 1997, 6, 191–202.
Triolo, A.; Arcamone, F. M.; Raffaelli, A.; Salvadori, P. Noncovalent Complexes Between DNA-Binding Drugs and Double Stranded Deoxyoligonucleotides: A Study by Ion Spray Mass Spectrometry. J. Mass Spectrom. 1997, 32, 1186–1194.
Schnier, P. D.; Klassen, J. S.; Strittmatter, E. F.; Williams, E. R. Activation Energies for Dissociation of Double Strand Oligonucleotide Anions: Evidence for Watson-Crick Base Pairing in Vacuo. J. Am. Chem. Soc. 1998, 120, 9605–9613.
Gabelica, V.; De Pauw, E.; Rosu, F. Interaction Between Antitumor Drugs and a Double Stranded Oligonucleotide Studies by Electrospray Ionization Mass Spectrometry. J. Mass Spectrom. 1999, 34, 1328–1337.
Gabelica, V.; Rosu, F.; Houssier, C.; De Pauw, E. Comparison Between Solution Phase Stability and Gas Phase Kinetic Stability of Oligodeoxynucleotide Duplexes. Rapid Commun. Mass Spectrom. 2000, 14, 464–467.
Wan, K. X.; Gross, M. L.; Shibue, T. Gas Phase Stability of Double Stranded Oligodeoxynucleotides and Their Noncovalent Complexes with DNA-Binding Drugs as Revealed by Collisional Activation in an Ion Trap. J. Am. Soc. Mass Spectrom. 2000, 11, 450–457.
Drahos, L.; Heeren, R.; Collette, C.; De Pauw, E.; Vekey, K. Thermal Energy Distribution Observed in Electrospray Ionization. J. Mass Spectrom. 1999, 34, 1373–1379.
Gabelica, V.; De Pauw, E. Comparison Between Solution Phase Stability and Gas Phase Stability of Oligodeoxynucleotide Duplexes. J. Mass Spectrom. 2001, 36, 397–402.
Gale, D. C.; Morris, A. K.; Sisk, E. C.; Fusciarelli, A. F.; Schwartz, B. L.; Harms, A. C.; Camp, D. G. II; Smith, R. D. Correlation Between ESI-MS, CID, and DNA Duplex Melting Temperature; Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta GA, May 1995, p 597.
Li, Y.; Zon, G.; Wilson, W. D. NMR and Molecular Modeling Evidence for a GA Mismatch Base Pair in a Purine Rich DNA Duplex. Proc. Natl. Acad. Sci. U.S.A. 1991, 88, 26–30.
SantaLucia, J.; Turner, D. H. Sructure of (rGGCGAGCC)2 in Solution from NMR and Restrained Molecular Dynamics. Biochemistry 1993, 32, 12612–12623.
SantaLucia, J.; Kierzek, R.; Turner, D. H. Effects of GA Mismatches on the Structure and Thermodynamics of RNA Internal Loops. Biochemistry 1990, 29, 8813–8819.
Aboul-ela, F.; Kohn, D.; Martin, F.; Tinoco, I. Base-Base Mismatches. Thermodynamics of Double Helix Formation for dCA3XA3G + dCT3YT3G (X,Y = A,C,G,T). Nucleic Acids Res. 1985, 13, 4811–4824.
Gautheret, D.; Konings, D.; Gutell, R. R. A Major Family of Motifs Involving GA Mismatches in Ribosomal RNA. J. Mol. Biol. 1994, 242, 1–8.
Chou, S.; Zhu, L.; Reid, B. R. Sheared Purine Pairing in Biology. J. Mol. Biol. 1997, 267, 1055–1067.
Wu, Q.; Gao, J.; Sigal, G. B.; Bruce, J. E.; Whitesides, G. M.; Smith, R. D. Carbonic Anhydrase-Inhibitor Binding: From Solution to the Gas Phase. J. Am. Chem. Soc. 1997, 119, 1157–1158.
Saenger, W. Principles of Nucleic Acid Structure Springer-Verlag: New York, 1984; 116–158.
Gotoh, O.; Takashira, Y. Stabilities of Nearest Neighbor Doublets in Double Helical DNA Determined by Fitting Calculated Melting Profiles to Observed Profiles. Biopolymers 1981, 20, 1033–1042.
Wolynes, P. G. Biomolecular Folding In Vacuo!!!(?). Proc. Natl. Acad. Sci. U.S.A. 1995, 92, 2426–2427.
Wood, T. D.; Chorush, R. A.; Wampler, F. M.; III.; Little, D. P.; O’Connor, P. B.; McLafferty, F. W. Gas-Phase Folding and Unfolding of Cytochrome C Cations. Proc. Natl. Acad. Sci. U.S.A. 1995, 92, 2426–2427.
SantaLucia, J.; Kierzek, R.; Turner, D. H. Context Dependence of Hydrogen Bond Free Energy Revealed by Substitutions in an RNA Hairpin. Science 1992, 256, 217–219.
Walter, A. E.; Wu, M.; Turner, D. H. The Stability and Structure of Tandem GA Mismatches in RNA Depend on Closing Base Pairs. Biochemistry 1994, 33, 11349–11354.
Greene, K. L.; Jones, R. L.; Li, Y.; Robinson, H.; Wang, A. H.; Zon, G.; Wilson, W. D. Solution Structure of a GA Mismatch DNA Sequence, d(CCATGAATGG)2, Determined by 2D NMR and Structural Refinement Methods. Biochemistry 1994, 33, 1053–1062.
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Published online July 28, 2004
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Yang, M.(., Thompson, R. & Hall, G. Comparative stability determination of oligonucleotide duplexes in gas and solution phase. J Am Soc Mass Spectrom 15, 1354–1359 (2004). https://doi.org/10.1016/j.jasms.2004.06.008
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DOI: https://doi.org/10.1016/j.jasms.2004.06.008