Tunable Liquid Chromatographic Separation of H/D Isotopologues Enabled by Aromatic π Interactions

Kanao, Eisuke; Kubo, Takuya; Naito, Toyohiro; Sano, Tomoharu; Yan, Mingdi; Tanaka, Nobuo; Otsuka, Koji

doi:10.1021/acs.analchem.9b05672

Cited by 13 publications

(6 citation statements)

References 64 publications

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“…S3), the 2-propanol gradient did not affect separation. According to these separation behaviors, it is assumed that the separation mechanisms in the fullerene-bonded columns are affected not only by the hydrophobic interaction but also by CH-π and/or OH-π interactions between fullerenes and Glcs, as they were in our previous study 46 .…”

Section: Resultsmentioning

confidence: 81%

“…Interestingly, the Glcs were still separated due to the increase of the glucose unit in both columns. Here, according to our previous studies, fullerenes effectively allowed π interactions, such as the CH-π and/or OH-π interactions 41,42,46 . For this comparison, the measurements were conducted for non-labelled saccharides with the applied columns and the results showed that the separation was achieved for using C60/C70 columns, but not for using C18 columns.…”

Section: Resultsmentioning

confidence: 99%

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Separation of saccharides using fullerene-bonded silica monolithic columns via π interactions in liquid chromatography

Kobayashi

Okada

Tokuda

et al. 2020

Sci Rep

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We report on a potential method to separate sugars by using the specific interaction between fullerenes and saccharides in liquid chromatography (LC). Aromatic rings with high electron density are believed to interact strongly with saccharides due to CH-π and/or OH-π interactions. In this study, the fullerene-bonded columns were used to separate saccharides by LC under aqueous conditions. As a result, 2-aminobenzamide-labeled glucose homopolymer (Glcs) was effectively separated by both C60 and C70 columns in the range of Glc-1 to Glc-20 and high blood glucose level being retained in greater quantity. Furthermore, similar separations were identified by LC-mass spectrometry with nonlabeled glucose homopolymers. Theoretical study based on molecular dynamics and DFT calculation demonstrated that a supramolecular complex of saccharide-fullerene was formed through CH-π and/or OH-π interactions, and that the interactions between saccharide and fullerene increase with the increase units of the saccharide. Additionally, the C60 column retained disaccharides containing maltose, trehalose, and sucrose. In this case, it was assumed that the retention rates were determined by the difference of the dipole moment in each saccharide. These results suggest that the dipoleinduced dipole interaction was dominant, and that maltose-with the higher dipole moment-was more strongly retained compared to other disaccharides having lower dipole moment.

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Section: Resultsmentioning

confidence: 81%

Section: Resultsmentioning

confidence: 99%

Separation of saccharides using fullerene-bonded silica monolithic columns via π interactions in liquid chromatography

Kobayashi

Okada

Tokuda

et al. 2020

Sci Rep

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“…The monolithic column was prepared following the protocols in the previous report. − A bare capillary column (2–3 m in length) was treated with a 1.0 M aqueous sodium hydroxide solution at 40 °C for 3 h. Then, the column was washed with water and acetone and then dried. Tetramethyl orthosilicate (TMOS, 56 mL) was added to a solution of polyethylene glycol (PEG, 11.9 g) and urea (9.0 g) in 0.01 M acetic acid (100 mL), and the mixture was stirred at 0 °C for 30 min.…”

Section: Methodsmentioning

confidence: 99%

Rational Strategy for Space-Confined Seeded Growth of ZnO Nanowires in Meter-Long Microtubes

Kamei

Hosomi

Kanao

et al. 2021

ACS Appl. Mater. Interfaces

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Seeded crystal growths of nanostructures within confined spaces offer an interesting approach to design chemical reaction spaces with tailored inner surface properties. However, such crystal growth within confined spaces tends to be inherently difficult as the length increases as a result of confinement effects. Here, we demonstrate a space-confined seeded growth of ZnO nanowires within meter-long microtubes of 100 μm inner diameter with the aspect ratio of up to 10 000, which had been unattainable to previous methods of seeded crystal growths. ZnO nanowires could be grown via seeded hydrothermal crystal growth for relatively short microtubes below the length of 40 mm, while any ZnO nanostructures were not observable at all for longer microtubes above 60 mm with the aspect ratio of 600. Microstructural and mass spectrometric analysis revealed that a conventional seed layer formation using zinc acetate is unfeasible within the confined space of long microtubes as a result of the formation of detrimental residual Zn complex compounds. To overcome this space-confined issue, a flow-assisted seed layer formation is proposed. This flow-assisted method enables growth of spatially uniform ZnO nanowires via removing residual compounds even for 1 m long microtubes with the aspect ratio of up to 10 000. Finally, the applicably of ZnO-nanowire-decorated long microtubes for liquid-phase separations was demonstrated.

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“…Thus, the deuterated analytes were able to be greatly retained by the stronger OH-π interactions. Finally, applying these opposing H/D isotope effects, we were able to demonstrate effective H/D isotopologue separations by utilizing the complementary action of OH-π and CH-π interactions [52].…”

Section: Liquid Chromatographic Strategies For the Separation Of Deut...mentioning

confidence: 99%

Studies on π Interactions in Liquid-Phase Separations

Kanao

2022

Chromatography

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π interactions have recently received considerable attentions due to principal factor governing molecular recognitions and self-assemble abilities, as accumulated in the database on proximate arrangements in structures of biological systems and organic functional materials. Therefore, further deep understanding and control of π interactions will greatly facilitate the development of new functional materials. Despite the importance of π interactions, they are still challenging to study because π interactions are much weaker than most other molecular interactions, such as hydrophobic interaction, hydrogen bonding, and electrostatic bonding. On the other hand, liquid chromatography (LC) is a powerful separation technique, which is able to distinguish the partition coefficients of solutes between the mobile and stationary phases, and can sensitively reflect the strength of molecular interactions. We investigated the properties of π interactions by developing new silica-monolithic capillary columns modified with carbon materials providing strong π interactions. In this focusing review, we introduce a few specific π interactions by columns modified with fullerenes and polycyclic aromatic hydrocarbons (PAHs), which showed strong π-π interactions due to spherical recognition and multiple CH-π interactions. Furthermore, π interactions can contribute to the separation of various samples, which are difficult to achieve by the available retention mechanisms. Briefly, we applied various π interactions to specific separation analyses, and we succeeded in separating halogenated compounds, H/D isotopologue pairs, and saccharides by effective π interactions. These results indicate that π interactions contribute to practical separation science, such as removal of environmental pollutants and quantitative determination of medicinal compounds.

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Tunable Liquid Chromatographic Separation of H/D Isotopologues Enabled by Aromatic π Interactions

Cited by 13 publications

References 64 publications

Separation of saccharides using fullerene-bonded silica monolithic columns via π interactions in liquid chromatography

Separation of saccharides using fullerene-bonded silica monolithic columns via π interactions in liquid chromatography

Rational Strategy for Space-Confined Seeded Growth of ZnO Nanowires in Meter-Long Microtubes

Studies on π Interactions in Liquid-Phase Separations

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