Vibrational excitation of adsorbed molecules by photoelectrons of very low energy: acrylonitrile on Cu (100)

2011 ◽  
Vol 13 (18) ◽  
pp. 8475 ◽  
Author(s):  
J. Tornero ◽  
H.H. Telle ◽  
G. García ◽  
A. González Ureña
Keyword(s):  
Vibrational Excitation ◽  
Low Energy ◽  
Adsorbed Molecules

scholarly journals The effect of adenine protonation on RNA phosphodiester backbone bond cleavage elucidated by deaza-nucleobase modifications and mass spectrometry

2019 ◽  
Vol 47 (14) ◽  
pp. 7223-7234 ◽  
Author(s):  
Elisabeth Fuchs ◽  
Christoph Falschlunger ◽  
Ronald Micura ◽  
Kathrin Breuker
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Vibrational Excitation ◽  
Bond Cleavage ◽  
Low Energy ◽  
Biological Processes ◽  
Phosphodiester Backbone ◽  
Collisionally Activated Dissociation ◽  
Rna Backbone ◽  
Ionic Hydrogen Bonds

Abstract The catalytic strategies of small self-cleaving ribozymes often involve interactions between nucleobases and the ribonucleic acid (RNA) backbone. Here we show that multiply protonated, gaseous RNA has an intrinsic preference for the formation of ionic hydrogen bonds between adenine protonated at N3 and the phosphodiester backbone moiety on its 5′-side that facilitates preferential phosphodiester backbone bond cleavage upon vibrational excitation by low-energy collisionally activated dissociation. Removal of the basic N3 site by deaza-modification of adenine was found to abrogate preferential phosphodiester backbone bond cleavage. No such effects were observed for N1 or N7 of adenine. Importantly, we found that the pH of the solution used for generation of the multiply protonated, gaseous RNA ions by electrospray ionization affects phosphodiester backbone bond cleavage next to adenine, which implies that the protonation patterns in solution are at least in part preserved during and after transfer into the gas phase. Our study suggests that interactions between protonated adenine and phosphodiester moieties of RNA may play a more important mechanistic role in biological processes than considered until now.

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