Letter: α,ω,N,N-Dimethylaminoalkylamines as possible derivatization agents for the analysis of small carbonyl compounds by low energy mass spectrometry

2016 ◽  
Vol 22 (3) ◽  
pp. 151 ◽  
Author(s):  
Roman Borisov ◽  
Dmitry Zhilyaev ◽  
Nikolai Polovkov ◽  
Vladimir Zaikin
2018 ◽  
Vol 89 (10) ◽  
pp. 103102 ◽  
Author(s):  
Lingling Chen ◽  
Ziwei Chen ◽  
Ziyuan Li ◽  
Jie Hu ◽  
Shan Xi Tian

2019 ◽  
Vol 47 (14) ◽  
pp. 7223-7234 ◽  
Author(s):  
Elisabeth Fuchs ◽  
Christoph Falschlunger ◽  
Ronald Micura ◽  
Kathrin Breuker

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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