Chiral differentiation of d- and l-isoleucine using permethylated β-cyclodextrin: Infrared multiple photon dissociation spectroscopy, ion-mobility mass spectrometry, and DFT calculations

Sung Sik Lee, Jae Ung Lee, Ju Hyeon Oh, Soojin Park, Yin Hong, Byeong Ki Min, Hyun Hee L. Lee, Hugh I. Kim, Xianglei Kong, Sungyul Lee, Han Bin Oh

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Chiral differentiation of protonated isoleucine (Ile) using permethylated β-cyclodextrin (perCD) in the gas-phase was studied using infrared multiple photon dissociation (IRMPD) spectroscopy, ion-mobility, and density functional theory (DFT) calculations. The gaseous protonated non-covalent complexes of perCD and d-Ile or l-Ile produced by electrospray ionization were interrogated by laser pulses in the wavenumber region of 2650 to 3800 cm -1 . The IRMPD spectra showed remarkably different IR spectral features for the d-Ile or l-Ile and perCD non-covalent complexes. However, drift-tube ion-mobility experiments provided only a small difference in their collision cross-sections, and thus a limited separation of the d- and l-Ile complexes. DFT calculations revealed that the chiral distinction of the d- and l-complexes by IRMPD spectroscopy resulted from local interactions of the protonated Ile with perCD. Furthermore, the theoretical results showed that the IR absorption spectra of higher energy conformers (by ∼13.7 kcal mol -1 ) matched best with the experimentally observed IRMPD spectra. These conformers are speculated to be formed from kinetic-trapping of the solution-phase conformers. This study demonstrated that IRMPD spectroscopy provides an excellent platform for differentiating the subtle chiral difference of a small amino acid in a cyclodextrin-complexation environment; however, drift-tube ion-mobility did not have sufficient resolution to distinguish the chiral difference.

Original languageEnglish
Pages (from-to)30428-30436
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number48
DOIs
Publication statusPublished - 2018 Jan 1

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ion mobility spectroscopy
Isoleucine
Cyclodextrins
Photons
Density functional theory
Mass spectrometry
Mass Spectrometry
Spectrum Analysis
mass spectroscopy
Spectroscopy
dissociation
Ions
density functional theory
Infrared radiation
photons
tubes
spectroscopy
Electrospray ionization
amino acids
ions

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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Chiral differentiation of d- and l-isoleucine using permethylated β-cyclodextrin : Infrared multiple photon dissociation spectroscopy, ion-mobility mass spectrometry, and DFT calculations. / Lee, Sung Sik; Lee, Jae Ung; Oh, Ju Hyeon; Park, Soojin; Hong, Yin; Min, Byeong Ki; Lee, Hyun Hee L.; Kim, Hugh I.; Kong, Xianglei; Lee, Sungyul; Oh, Han Bin.

In: Physical Chemistry Chemical Physics, Vol. 20, No. 48, 01.01.2018, p. 30428-30436.

Research output: Contribution to journalArticle

Lee, Sung Sik ; Lee, Jae Ung ; Oh, Ju Hyeon ; Park, Soojin ; Hong, Yin ; Min, Byeong Ki ; Lee, Hyun Hee L. ; Kim, Hugh I. ; Kong, Xianglei ; Lee, Sungyul ; Oh, Han Bin. / Chiral differentiation of d- and l-isoleucine using permethylated β-cyclodextrin : Infrared multiple photon dissociation spectroscopy, ion-mobility mass spectrometry, and DFT calculations. In: Physical Chemistry Chemical Physics. 2018 ; Vol. 20, No. 48. pp. 30428-30436.
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abstract = "Chiral differentiation of protonated isoleucine (Ile) using permethylated β-cyclodextrin (perCD) in the gas-phase was studied using infrared multiple photon dissociation (IRMPD) spectroscopy, ion-mobility, and density functional theory (DFT) calculations. The gaseous protonated non-covalent complexes of perCD and d-Ile or l-Ile produced by electrospray ionization were interrogated by laser pulses in the wavenumber region of 2650 to 3800 cm -1 . The IRMPD spectra showed remarkably different IR spectral features for the d-Ile or l-Ile and perCD non-covalent complexes. However, drift-tube ion-mobility experiments provided only a small difference in their collision cross-sections, and thus a limited separation of the d- and l-Ile complexes. DFT calculations revealed that the chiral distinction of the d- and l-complexes by IRMPD spectroscopy resulted from local interactions of the protonated Ile with perCD. Furthermore, the theoretical results showed that the IR absorption spectra of higher energy conformers (by ∼13.7 kcal mol -1 ) matched best with the experimentally observed IRMPD spectra. These conformers are speculated to be formed from kinetic-trapping of the solution-phase conformers. This study demonstrated that IRMPD spectroscopy provides an excellent platform for differentiating the subtle chiral difference of a small amino acid in a cyclodextrin-complexation environment; however, drift-tube ion-mobility did not have sufficient resolution to distinguish the chiral difference.",
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AU - Oh, Ju Hyeon

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AU - Min, Byeong Ki

AU - Lee, Hyun Hee L.

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AU - Oh, Han Bin

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