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- W3047234672 abstract "Structures, thermochemistries, reactivities, and kinetics of chemical systems in the gas phase can be determined by a variety of ion activation techniques. The internal energy of ions can be increased by colliding the accelerated ions with a target gas, collision-induced dissociation (CID). This technique can lead to a full or partial structural identification, and also to the relative stabilities of the ion clusters. Ions in the gas phase may reach a dissociation threshold by absorbing multiple photons from the laser radiation if the laser frequency is resonant with a vibrational mode which is called infrared multiphoton dissociation (IRMPD). This technique turns into IRMPD spectroscopy by varying the laser frequency and recording the resultant fragments as a function of laser frequency. Blackbody infrared radiative dissociation (BIRD) is another photodissociation technique used in this work that is well suited to slowly activate weakly-bound non-covalent interactions in order to determine their thermochemistries and also gain kinetic insights. Theoretical techniques have been used along with these activation techniques as a powerful complementary tool.This work provides physical chemistry insights about guanine tetrads and quadruplexes in the gas phase. The first phase of this research focuses on the alkali metal G-tetrads, M(9-eG)₄⁺ (M=Li, Na, K, Rb, Cs; 9eG = 9-ethylguanine). After their gas phase formation, their structures, stabilities, and energetics were examined by a combination of SORI-CID, IRMPD spectroscopy, and computational chemistry. The role of hydrogen bonding, the size of cation, and electrostatic interactions in the stability and structures were also examined. The formation of alkali metal G-quadruplexes, (M(9eG)₈⁺ (M = Na, K, Rb, Cs), was pursued in the next phase. The BIRD technique, in conjunction with master equation modeling, was applied to determine the binding energies and transition state nature of these G-quadruplexes. IRMPD spectroscopy, along with theoretical techniques, was used for structural elucidation. In the final step, gas phase formation of larger G-quadruplexes was assessed. The K₂(9-ethylguanine)₁₂⁺ quadruplex was successfully generated and isolated in the gas phase. BIRD and SORI-CID techniques were used to determine the quadruplex binding energies and gas phase stability, respectively. The structure of this quadruplex was determined by IRMPD spectroscopy and computational chemistry." @default.
- W3047234672 created "2020-08-10" @default.
- W3047234672 creator A5004785429 @default.
- W3047234672 date "2017-09-01" @default.
- W3047234672 modified "2023-09-27" @default.
- W3047234672 title "Structures and energetics of guanine tetrads and quadruplexes isolated in the gas phase" @default.
- W3047234672 hasPublicationYear "2017" @default.
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