Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline: Chemical exchange 2DIR spectroscopic investigations

Kyung Koo Lee; Kwang Hee Park; Cheonik Joo; Hyeok Jun Kwon; Hogyu Han; Jeong Hyon Ha; Sungnam Park; Minhaeng Cho

doi:10.1016/j.chemphys.2011.04.024

Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline: Chemical exchange 2DIR spectroscopic investigations

Kyung Koo Lee, Kwang Hee Park, Cheonik Joo, Hyeok Jun Kwon, Hogyu Han, Jeong Hyon Ha, Sungnam Park, Minhaeng Cho

Research output: Contribution to journal › Article › peer-review

21 Citations (Scopus)

Abstract

The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C ^γ-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl ₃. Using the two-dimensional infrared (2DIR) and polarization- controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.

Original language	English
Pages (from-to)	23-29
Number of pages	7
Journal	Chemical Physics
Volume	396
Issue number	1
DOIs	https://doi.org/10.1016/j.chemphys.2011.04.024
Publication status	Published - 2012 Mar 2

Bibliographical note

Funding Information:
This work was supported by the NRF Grant (No. 2010-0005020 ) to S.P., the NRF (No. 2009-0078897 and 2010-0020209) and KBSI (T31401) Grants to M.C., and the NRF (No. 2010-0022070) and KBSI (T31401) grants to H.H.

Keywords

Azido stretch mode
Proline dynamics
Two-dimensional infrared spectroscopy

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1016/j.chemphys.2011.04.024

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title = "Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline: Chemical exchange 2DIR spectroscopic investigations",

abstract = "The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C γ-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl 3. Using the two-dimensional infrared (2DIR) and polarization- controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.",

keywords = "Azido stretch mode, Proline dynamics, Two-dimensional infrared spectroscopy",

author = "Lee, {Kyung Koo} and Park, {Kwang Hee} and Cheonik Joo and Kwon, {Hyeok Jun} and Hogyu Han and Ha, {Jeong Hyon} and Sungnam Park and Minhaeng Cho",

note = "Funding Information: This work was supported by the NRF Grant (No. 2010-0005020 ) to S.P., the NRF (No. 2009-0078897 and 2010-0020209) and KBSI (T31401) Grants to M.C., and the NRF (No. 2010-0022070) and KBSI (T31401) grants to H.H. ",

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doi = "10.1016/j.chemphys.2011.04.024",

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T1 - Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline

T2 - Chemical exchange 2DIR spectroscopic investigations

AU - Lee, Kyung Koo

AU - Park, Kwang Hee

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AU - Kwon, Hyeok Jun

AU - Han, Hogyu

AU - Ha, Jeong Hyon

AU - Park, Sungnam

AU - Cho, Minhaeng

N1 - Funding Information: This work was supported by the NRF Grant (No. 2010-0005020 ) to S.P., the NRF (No. 2009-0078897 and 2010-0020209) and KBSI (T31401) Grants to M.C., and the NRF (No. 2010-0022070) and KBSI (T31401) grants to H.H.

PY - 2012/3/2

Y1 - 2012/3/2

N2 - The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C γ-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl 3. Using the two-dimensional infrared (2DIR) and polarization- controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.

AB - The azido group in 4-azidoproline (Azp) derivative, SA (Ac-(4S)-Azp-NHMe), can form an intramolecular electrostatic interaction with the backbone peptide in the s-trans and C γ-endo conformations of SA. As a result, the azido group exists as two forms, bound and free, which are defined by the presence and absence of such interaction, respectively. The bound and free azido forms are spectrally resolved in the azido IR spectrum of SA in CHCl 3. Using the two-dimensional infrared (2DIR) and polarization- controlled IR pump-probe methods, we investigated the internal rotational and orientational relaxation dynamics of the azido group and determined the internal rotational time constant of the azido group to be 5.1 ps. The internal rotational motion is found to be responsible for the early part of the orientational relaxation of the azido group in SA. Thus, the femtosecond 2DIR spectroscopy is shown to be an ideal tool for studying ultrafast conformational dynamics of SA.

KW - Azido stretch mode

KW - Proline dynamics

KW - Two-dimensional infrared spectroscopy

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Ultrafast internal rotational dynamics of the azido group in (4S)-azidoproline: Chemical exchange 2DIR spectroscopic investigations

Abstract

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Keywords

ASJC Scopus subject areas

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