期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 21, 期 28, 页码 15319-15326出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c9cp01651a
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资金
- Natural Sciences and Engineering Research Council (NSERC) of Canada
- Canada Foundation for Innovation (CFI)
- Industrial Research and Innovation Fund (IRIF)
- Bruker
A combination of experimental trapped-ion mass spectrometric studies and computational chemistry has been used in the present work to assess the intrinsic properties of the potassiated 9-ethylguanine (9eG) self-assembled quadruplex, K-2(9eG)(12)(2+), in the gas phase. Infrared multiple photon dissociation (IRMPD) spectroscopy in the N-H/C-H stretching region (2700-3800 cm(-1)) revealed that this G-quadruplex is a sandwich-type structure with two G-tetrads sandwiching each of the two K+, very similar to the structure determined previously for the K(9eG)(8)(+) complexes. The stability of K-2(9eG)(12)(2+) toward unimolecular dissociation and its binding energy were examined using energy-resolved sustained off-resonance collision induced dissociation (SORI-CID) and blackbody infrared radiative dissociation (BIRD) kinetics experiments. SORI-CID experiments showed that the self-assembled K-2(9eG)(12)(2+) complex undergoes charge separation forming K(9eG)(8)(+) and K(9eG)(4)(+) compared to K(9eG)(8)(+) which loses neutral 9eG. More interestingly, K-2(9eG)(12)(2+) is more stable toward unimolecular dissociation activated by SORI-CID than the K(9eG)(8)(+) complex. Temperature dependent BIRD kinetics for K-2(9eG)(12)(2+) were consistent with energy-resolved SORI-CID results showing K-2(9eG)(12)(2+) to have an activation energy of 225 +/- 15 kJ mol(-1), approximately 50 kJ mol(-1) greater than that determined for K(9eG)(8)(+). The extra stability of K-2(9eG)(12)(2+) is apparently not thermodynamic stability, but most likely due to an energy barrier for dissociation.
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