Soft X-ray Absorption Spectroscopy for Observing Element-specific Intermolecular Interaction in Solution Chemistry

Nagasaka, Masanari; Kosugi, Nobuhiro

doi:10.1246/cl.200938

Cited by 16 publications

(12 citation statements)

References 97 publications

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“…XAS was measured at the soft X-ray undulator beamline BL3U at the UVSOR-III Synchrotron . The detail of the transmission-type liquid flow cell for XAS of liquid samples was described previously. , The liquid cell is at an ambient pressure in helium gas, where a liquid layer is sandwiched between two Si 3 N 4 membranes with the thickness of 100 nm. For appropriate absorbance of soft X-rays, the liquid thickness is controlled by adjusting the helium pressure around the liquid cell.…”

Section: Methodsmentioning

confidence: 99%

Hydrophobic Cluster Formation in Aqueous Ethanol Solutions Probed by Soft X-ray Absorption Spectroscopy

et al. 2022

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Hydrophobic cluster structures in aqueous ethanol solutions at different concentrations have been investigated by soft X-ray absorption spectroscopy (XAS). In the O K-edge XAS, we have found that hydrogen bond structures among water molecules are enhanced in the middle-concentration region by the hydrophobic interaction of the ethyl groups in ethanol. In the C K-edge XAS, the lower energy features arise from a transition from the terminal methyl C 1s electron to an unoccupied orbital of 3s Rydberg character, which is sensitive to the nearest-neighbor intermolecular interactions. From the comparison of C K-edge XAS with the inner-shell calculations, we have found that ethanol clusters are easily formed in the middle-concentration region due to the hydrophobic interaction of the ethyl group in ethanol, resulting in the enhancement of the hydrogen bond structures among water molecules. This behavior is different from aqueous methanol solutions, where the methanol–water mixed clusters are more predominant in the middle-concentration region due to the relatively weak hydrophobic interactions of the methyl group in methanol.

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Section: Methodsmentioning

confidence: 99%

Hydrophobic Cluster Formation in Aqueous Ethanol Solutions Probed by Soft X-ray Absorption Spectroscopy

et al. 2022

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“…The XAS experiment was performed at the soft X-ray undulator beamline BL3U at the UVSOR-III Synchrotron . A detailed description of the liquid cell for XAS in transmission mode is available elsewhere. , The liquid cell was in an ambient pressure of helium gas, where a liquid layer was sandwiched between two SiC membranes with a thickness of 100 nm. Liquid samples were exchanged by using a tubing pump without changing the position of the liquid cell.…”

Section: Methodsmentioning

confidence: 99%

Solvent Effects in the Ultraviolet and X-ray Absorption Spectra of Pyridazine in Aqueous Solution

et al. 2021

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Electrostatic interaction of the solvent with the solute and fluctuations of the solvent configurations may make excitation energies of the solute different from those in the gas phase. These effects may dominate photoinduced or chemical reaction dynamics in solution systems and can be observed as shifts or broadening of peaks in absorption spectra. In this work, the nitrogen K-edge X-ray absorption spectra were measured for pyridazine in the gas phase and in aqueous solution. The ultraviolet and X-ray absorption spectra of pyridazine in aqueous solution, as well as those in the gas phase, were then calculated with models based on the algebraic−diagrammatic construction through second order [ADC(2)] with the resolution-of-identity (RI) approximation and compared with the spectra obtained in experiments. For aqueous solution, explicit local solvation structures were extracted from an ab initio molecular dynamics (AIMD) trajectory of pyridazine in bulk water, and RI-ADC(2) was combined with the conductor-like screening model (COSMO). The experimental absorption spectra of pyridazine in aqueous solution were reproduced with good accuracy by theoretical treatment of an ensemble containing the explicit local solvation structures of pyridazine with relevant water molecules combined with the COSMO solvation model of water for long-range solvation.

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“…24,25 Therefore, we measured the C K-edge spectra for luciferin at pH 7 and 10 using a soft X-ray spectroscopy measurement system developed by Nagasaka and Kosugi. 26,27 To assign C K-edge spectra, the characteristics of the molecular orbitals (MOs) that contribute to peaks in experimental spectra should be obtained. According to the previous studies, 25 the peaks with high intensity in the UV absorption spectra consist of the excitations whose main configuration is the transition to a π* type vacant orbital.…”

Section: Introductionmentioning

confidence: 99%

“…We focus on X-ray absorption spectra (XAS) as a method for investigating the difference in the electronic structure between the OH and the O – groups in luciferin. In recent years, XAS has been used to study the excited states of organic compounds in aqueous solution. – Nagasaka and Kosugi , reported O, N, and C K-edge spectra for liquid pyridine, liquid benzene, and aqueous acetonitrile solutions. Akazawa et al measured the XAS of aqueous cellobiose.…”

Section: Introductionmentioning

confidence: 99%

“…The aim of this paper is to elucidate the difference in 6′C 1s excitation between luciferin with C–OH bonds and with C–O – bonds in aqueous solutions. Because the p K a value for the hydroxy group on luciferin is 8.7, the most abundant species at pH 7 is luciferin anion, and that at pH 10 is luciferin dianion. , Therefore, we measured the C K-edge spectra for luciferin at pH 7 and 10 using a soft X-ray spectroscopy measurement system developed by Nagasaka and Kosugi. , …”

Section: Introductionmentioning

confidence: 99%

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Experimental and Theoretical Study for Core Excitation of Firefly Luciferin in Carbon K-Edge Spectra

Kudo,

Kumaki,

Nagasaka

et al. 2024

J. Phys. Chem. A

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Carbon (C) K-edge X-ray absorption spectra for firefly luciferin were measured and assigned using time-dependent density functional theoretical calculations for luciferin anion and dianion to elucidate the effect of hydroxy-group deprotonation. It was found that the C K-edge spectra for luciferin had four characteristic peaks. The effect of deprotonation of the hydroxy group appears in the energy difference of the first and second peaks of these spectra. This energy difference is 1.0 eV at pH 7 and 2.3 eV at pH 10. The deprotonation of the hydroxy group can be distinguished based on the soft X-ray absorption spectra.

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Soft X-ray Absorption Spectroscopy for Observing Element-specific Intermolecular Interaction in Solution Chemistry

Cited by 16 publications

References 97 publications

Hydrophobic Cluster Formation in Aqueous Ethanol Solutions Probed by Soft X-ray Absorption Spectroscopy

Hydrophobic Cluster Formation in Aqueous Ethanol Solutions Probed by Soft X-ray Absorption Spectroscopy

Solvent Effects in the Ultraviolet and X-ray Absorption Spectra of Pyridazine in Aqueous Solution

Experimental and Theoretical Study for Core Excitation of Firefly Luciferin in Carbon K-Edge Spectra

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