Cryogenic ion spectroscopy of adenine complexes containing alkali metal cations

Eun, Han Jun; Ishiuchi, Shun‐ichi; Baek, Ji Young; Lee, Seulgi; Heo, Jiyoung; Fujii, Masaaki; Kim, Nam Joon

doi:10.1039/d1cp00312g

Cited by 2 publications

(4 citation statements)

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“…The exclusion of NaCl and other solutes by ice to its surface quasi-liquid layer (QLL) has been known for a long time. − This layer is the substrate for intense chemical reactivity. In analogy to that, the surface and subsurface of cold aerosols may host similar reactivity. , We present two examples that demonstrate the significance of the dynamics and thermodynamics of NaCl and other ions on the ice QLL. The first example is the effect of NaCl in the photolysis reactions of adsorbed polycyclic aromatic hydrocarbons. , The presence of NaCl in QLL has been found to affect the kinetics of the photolysis reactions, but the manner in which it intervenes is still unknown.…”

Section: Introductionmentioning

confidence: 83%

“…In analogy to that, the surface and subsurface of cold aerosols may host similar reactivity. 35,39 We present two examples that demonstrate the significance of the dynamics and thermodynamics of NaCl and other ions on the ice QLL. The first example is the effect of NaCl in the photolysis reactions of adsorbed polycyclic aromatic hydrocarbons.…”

Section: ■ Introductionmentioning

confidence: 97%

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Salt Enrichment and Dynamics in the Interface of Supercooled Aqueous Droplets

et al. 2022

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The interconversion reaction of NaCl between the contact-ion pair (CIP) and the solvent-separated ion pair (SSIP) as well as the free-ion state in cold droplets has not yet been investigated. We report direct computational evidence that the lower is the temperature, the closer to the surface the ion interconversion reaction takes place. In supercooled droplets the enrichment of the subsurface in salt becomes more evident. The stability of the SSIP relative to the CIP increases as the ion-pairing is transferred toward the droplet’s outer layers. In the free-ion state, where the ions diffuse independently in the solution, the number density of Cl– shows a broad maximum in the interior in addition to the well-known maximum in the surface. In the study of the reaction dynamics, we find a weak coupling between the interionic NaCl distance reaction coordinate and the solvent degrees of freedom, which contrasts with the diffusive crossing of the free energy barrier found in bulk solution modeling. The H2O self-diffusion coefficient is found to be at least an order of magnitude larger than that in the bulk solution. We propose to exploit the enhanced surface ion concentration at low temperature to eliminate salts from droplets in native mass spectrometry ionization methods.

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Section: Introductionmentioning

confidence: 83%

Section: ■ Introductionmentioning

confidence: 97%

Salt Enrichment and Dynamics in the Interface of Supercooled Aqueous Droplets

et al. 2022

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“…20 UV photodissociation (UVPD) spectra of adenine complexes with alkali metal cations (M + A) were also investigated using cryogenic ion spectroscopy. 21 All M + A ions were present as single isomers in a cryogenic ion trap, where M + ions were bound to not canonical 9H-adenine (9A) but a rare tautomer, 7H-adenine (7A), producing M + 7A ions. Moreover, the UVPD spectra exhibited well-resolved vibronic bands, suggesting long excitedstate lifetimes of M + 7A.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In particular, the presence of alkali metal cations (M + , M = Li, Na, K, Rb, and Cs) increases the yields of rare tautomers. − Nucleobase complexes containing alkali metal cations have been extensively studied as a model system to elucidate the roles of alkali metal cations in the formation of rare tautomers at a molecular level. − Recently, cryogenic ion spectroscopy has become a powerful tool to investigate the structures and excited-state properties of metal ion complexes in the gas phase, which are produced by electrospray ionization (ESI) and stored in a cryogenic ion trap. − UV photofragmentation spectra of cold cytosine–Na + (CytNa + ), CytK + , and CytAg + complexes were obtained and analyzed through comparison with theoretical calculations of the ground and excited states . UV photodissociation (UVPD) spectra of adenine complexes with alkali metal cations (M + A) were also investigated using cryogenic ion spectroscopy . All M + A ions were present as single isomers in a cryogenic ion trap, where M + ions were bound to not canonical 9 H -adenine (9A) but a rare tautomer, 7 H -adenine (7A), producing M + 7A ions.…”

Section: Introductionmentioning

confidence: 99%

Cryogenic Ion Spectroscopy of Protonated and Sodiated Methyladenine Derivatives

et al. 2023

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Ultraviolet photodissociation (UVPD) spectra of protonated 9-methyladenine (H + 9MA), protonated 7-methyl adenine (H + 7MA), protonated 3-methyladenine (H + 3MA), and sodiated 7methyladenine (Na + 7MA) near the origin bands of the S 0 −S 1 transition were obtained using cryogenic ion spectroscopy. The UV− UV hole burning, infrared (IR) ion-dip, and IR-UV double resonance spectra showed that all the ions were present as single isomers in a cryogenic ion trap. The UVPD spectrum of H + 9MA exhibited only a broad absorption band, whereas the spectra of H + 7MA, H + 3MA, and Na + 7MA displayed moderately or well-resolved vibronic bands. Potential energy profiles were computed to understand the reason for the different bandwidths of the vibronic bands in the spectra. The broadening of the bands was correlated with the slopes between the Franck−Condon point and the conical intersection between the S 1 and S 0 states in the potential energy profiles, thus reflecting the deactivation rates in the S 1 state.

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Cryogenic ion spectroscopy of adenine complexes containing alkali metal cations

Abstract: Cryogenic ion spectroscopy was used to characterize adenine complexes containing alkali metal cations (M+A, M=Cs, Rb, K, Na, and Li) produced by electrospray ionization. The ultraviolet (UV) photodissociation spectra of...

Cited by 2 publications

References 40 publications

Salt Enrichment and Dynamics in the Interface of Supercooled Aqueous Droplets

Salt Enrichment and Dynamics in the Interface of Supercooled Aqueous Droplets

Cryogenic Ion Spectroscopy of Protonated and Sodiated Methyladenine Derivatives

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